Azo compounds having at least one 6-hydroxypyrid-2-one coupling component radical metal complexes thereof and intermediates therefor

ABSTRACT

A compound of formula I ##STR1## in metal-free; 1:1 or 1:2 metal complex form and, when an acid group is present, in free acid or acid addition salt form, in which R 1  is hydrogen or --N═N--D where D is a diazo component and R, T and B are organic radicals defined in the text.

This application is a continuation-in-part of application Ser. No.06/485,212, filed Apr. 15, 1983 and now abandoned.

The invention relates to compounds suitable for use as dyestuffs and tointermediates for making such dyestuffs.

According to the invention there are provided compounds of formula I##STR2## in metal-free or 1:1 or 1:2 metal complex form, and, in freeacid or acid addition salt form,

in which

R is hydrogen; C₁₋₄ alkyl; C₅₋₆ cycloalkyl unsubstituted or substitutedby one or two C₁₋₄ alkyl groups; phenyl, benzyl or phenylethyl, thephenyl group of the latter three substituents being unsubstituted orsubstituted by one or two groups selected from methyl, ethyl,methoxy andethoxy,

T is hydrogen, --CN, ##STR3## --COOR₄ ; --CON(R₆)₂, --SO₂ N(R₅)₂ ;##STR4## B is --A--NH--R₂ ; hydrogen; C₁₋₄ alkyl unsubstituted orsubstituted by C₁₋₄ alkoxy; C₂₋₄ alkyl substituted by hydroxy; C₅₋₆cycloalkyl unsubstituted or substituted by one to three C₁₋₄ alkylgroups; phenyl(C₁₋₃ alkyl), the phenyl group of which is unsubstitutedor substituted by one to three groups selected from C₁₋₄ alkyl, C₁₋₄alkoxy and halogen; --A₄ '--N(R₇)₂ ; --A₄ --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ or--N(R₇)₂ ;

R₁ is a group α ##STR5## or, when B is --A--NH--R₂, hydrogen or--N═N--D; where

X_(a) is --O--, --N(R₅)-- or --S--;

R₃ is hydrogen, C₁₋₄ alkyl, --N(R₅)₂ or --CON(R₅)₂ ;

R₄ is C₁₋₆ alkyl or phenyl(C₁₋₃ alkyl);

R₅ is hydrogen or C₁₋₄ alkyl; or when two R₅ 's are present attached toa nitrogen atom both R₅ 's together with the N-atom to which they areattached may form a saturated ring which contains one to three heteroatoms;

R₆ is C₁₋₄ alkyl;

A₁ is a residue of a tetrazo component;

R₆₀ is OH and R_(60a) is hydrogen or NH₂ or R₆₀ is NH₂ and R_(60a) isOH;

n is 0, 1 or 2;

A₄ is C₂₋₈ alkylene or C₂₋₈ alkenylene;

A₄ ' is C₁₋₈ alkylene or C₂₋₈ alkenylene;

D is a diazo component;

where

A is C₂₋₈ alkylene which may be interrupted by up to two hetero atoms;C₂₋₈ alkenylene which may be interrupted by up to two hetero atoms;phenylene or cyclohexylene;

R₂ is ##STR6## q is 0 or 1; R₁₁ is hydrogen, halogen, nitro C₁₋₄ alkylor C₁₋₄ alkoxy;

R₁₂ is ##STR7## --CO(CH₂)_(a) --Z or hydrogen,

a is an integer 1 to 3.

R₁₄ is an aliphatic, cycloaliphatic, aromatic or heterocyclic aminegroup in which the N-atom is attached to the triazinyl ring;

R₁₃ is a significance of R₁₄, halogen, --OH, --NH₂ C₁₋₄ alkoxy, phenylor ##STR8## A₂ is a linear or branched C₂₋₆ alkylene or --N*H--CO--CH₂-- where the starred N-atom is attached to the --NR₅ group;

Z is --N(R₇)₂ or --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖

each R₇, independently, is hydrogen, C₁₋₆ alkyl, C₂₋₆ alkyl substitutedby an halogen, --OH or --CN group, phenyl(C₁₋₃ alkyl), the phenyl ringof which is unsubstituted or substituted by 1 to 3 groups selected fromhalogen, C₁₋₄ alkyl and C₁₋₄ alkoxy; or C₅₋₆ cycloalkyl, unsubstitutedor substituted by 1 or 3 C₁₋₄ alkyl groups;

or both R₇ 's together with the N-atom to which they are attached form a5- or 6-membered saturated ring which contains one to three hetero atoms(referred to hereafter as the "cyclic significances of R₇ ");

each R₈ independently, has one of the non-cyclic significances of R₇except hydrogen and R₉ is C₁₋₄ alkyl unsubstituted or substituted byphenyl or

both R₈ 's, R₉ and the N-atom to which they are attached form apyridinium group (attached by its N-atom) unsubstituted or substitutedby one or two C₁₋₄ alkyl groups; or a 5- or 6-membered saturated ringwhich contains 1 to 3 hetero atoms;

R₁₇ is hydrogen, ##STR9## --N═N--K₁ ; --N═N--A₁₀ --N═N--K₁ or ##STR10##where X_(o) is a bridging group and A₁₀ has a significance of A₁ definedabove or is a coupling/diazo component

K₁ is a diazo or coupling component;

R₁₉ is hydrogen or when R₁₇ is --N═N--K₁ or --N═N--A₁₀ ----N═N--K₁additionally --OH, --NH₂, C₁₋₄ alkyl-carbonylamino, benzoylamino orphenylamino, the phenyl group of the latter two substituents beingunsubstituted or substituted by 1 or 2 substituents selected fromhalogen, --NO₂, --NH₂, C₁₋₄ alkyl and C₁₋₄ alkoxy;

R₂₀ is --NR₅)_(q) Q₁ --N(R₇)₂ ; --NR₅)_(q) Q₂ --N.sup.⊖ (R₈)₂ R₉ A.sup.⊖or ##STR11## Q₁ is --CH₂ CO--, --NHCOCH₂ -- or C₂₋₆ alkylene where thestarred atom is attached to --NR₅ (if present)

or the phenyl ring to which R₂₀ is attached;

Q₂ is --CONHCOCH₂ -- or a significance of Q₁ ;

A.sup.⊖ is a non-chromophoric anion;

with the provisos that:

(i) when the compound of formula I is sulpho-free at least onewater-solubilising basic or cationic group is present if the compound offormula I is a monoazo compound; and at least two water-solubilisinggroups are present if the compound of formula I is other than monoazo;

(ii) when one or more sulpho groups are present in the compound offormula I, the number of cationic and basic groups present is at leastthe number of sulpho groups+1;

(iii) when

B is --A--NH--R₂, where A is C₂₋₈ alkylene;

R₁ on the same pyridone ring is hydrogen and

T on the same pyridone ring is --CN, then R₂ on the same pyridone ringis not hydrogen. Preferably in the compounds of formula I when B is--A--NH--R₂ then group B is sulpho-free.

Preferably A₁₀ has only a significance of A₁.

In the specification halogen means fluorine, chlorine, bromine oriodine, preferably chlorine.

For the avoidance of doubt the group D--N═N-- includes the group α.

Where any symbol appears more than once in a formula unless indicated tothe contrary its significances are independent of one another.

Any alkyl, alkylene or alkenylene present is linear or branched unlessindicated otherwise. The alkyl group of any alkoxy group is linear orbranched unless indicated to the contrary.

Any sulpho group present may be in free acid or salt form when in saltform the --SO₃.sup.⊖ is balanced by a cation M.sup.⊕ (where M.sup.⊕ is anon-chromophoric cation for example Na.sup.⊕, K.sup.⊕ or NH₄.sup.⊕) orby a protonated basic non-cationic group or by a cationic group in themolecule.

Unless otherwise indicated the preferred significance of a variableapplies to that variable regardless of where the variable is set forthin the specification.

Any aliphatic amine group is preferably a mono C₁₋₄ alkyl- or a di-(C₁₋₄alkyl)amino group. Each alkyl group independently may be substituted by1 to 3 substituents independently selected from halogen, phenyl, hydroxyand C₅₋₆ cycloalkyl, but is preferably unsubstituted or monosubstitutedby phenyl or hydroxy, any hydroxy being other than in the α-position.

Any cycloaliphatic amine group present is preferably C₅₋₆cycloalkylamine, the cycloalkyl group of which may be substituted by oneor two C₁₋₂ alkyl groups.

Any aromatic amine group present is preferably aniline, the phenyl ringof which is unsubstituted or substituted by one to three substituentsselected from C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, hydroxy and phenoxy.

Any heterocyclic amino group present (or 5- or 6-membered heterocyclicring) is preferably a pyridine, triazine, pyridazine, pyrimidine, orpyrazine group or a group of the formula ##STR12## (when unsaturated) ora morpholine, pyrrolidine, piperidine, piperazine group (whensaturated). Each group may be substituted by one to three R₆ groups,

R is preferably R' where R' is methyl, ethyl, unsubstituted phenyl,unsubstituted benzyl or unsubstituted cyclohexyl. More preferably R isR" where R" is methyl or unsubstituted phenyl.

T is preferably T' where T' is hydrogen, cyano, ##STR13## or CON(R₅ ')₂,where R₃ ' and R₅ ' are defined below. More preferably T is T" where T"is cyano or ##STR14## where R₃ " is defined below.

B is preferably B' where B' is --A'--NH--R₂ ', hydrogen, --CH₃, --C₂ H₅,--C₂ H₄ OH, unsubstituted cyclohexyl, benzyl, --(CH₂)₁₋₃ N(R₇ ')₂ or--(CH₂)₂₋₃ N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, where the symbols are definedbelow. B is more preferably B" where B" is --A"--NH--R₂ ", hydrogen,--CH₃, --C₂ H₅, benzyl, --(CH₂)_(b) N(R₇ ")₂ or --(CH₂)_(b) --N.sup.⊕(R₈)₂ R₉ A.sup.⊖, where the symbols are defined below and b is 2 or 3.

R₁ is preferably R₁ ' where R₁ ' is ##STR15## or when B is --A--NH--R₂,hydrogen or --N═N--D'; and where the symbols are defined below.

Preferably A is A' where A' is C₂₋₈ alkylene or unsubstituted phenylene.More preferably A is A" where A" is 1,2-ethylene, 1,3-propylene orunsubstituted meta or para phenylene.

Preferably R₂ is R₂ ' where R₂ ' is a group of formula ##STR16## wherethe symbols R₁₁ ' and R₁₂ ' are defined below. More preferably R₂ is R₂" where R₂ " is ##STR17## where R₁₂ " is defined below.

Preferably R₃ is R₃ ' where R₃ ' is hydrogen, methyl, ethyl, --NH₂ or--N(CH₃)₂. More preferably R₃ is R₃ " where R₃ " is hydrogen or methyl.

Preferably R₅ is R₅ ' where R₅ ' is hydrogen, methyl or ethyl.Preferably R₅ " is hydrogen or methyl.

Preferably R₆ is R₆ ' where R₆ ' is methyl or ethyl.

Preferably R₇ is R₇ ' where R₇ ' is hydrogen, linear or branched C₁₋₆alkyl, unbranched hydroxy C₂₋₃ alkyl, benzyl, 2-cyanoethyl or both R₇''s together with the N-atom to which they are attached form anunsubstituted pyrrolidine, piperidine, morpholine, piperazine orN-methylpiperazine group.

More preferably R₇ is R₇ " where R₇ " is hydrogen, methyl, ethyl,2-hydroxyethyl or both R₇ "'s together with the N-atom to which they areattached form an unsubstituted morpholine, piperidine, piperazine orN-methylpiperazine group;

Preferably R₈ is R₈ ' where R₈ ' is one of the significances of R₇ 'except hydrogen and R₉ is R₉ ' where R₉ ' is methyl, ethyl, propyl orbenzyl or both R₈ 's and R₉ ' together with the N-atom to which they areattached from a pyridinium ring unsubstituted or substituted by one ortwo methyl groups or a group β ##STR18## where Z_(o) is --O--, a directbond, --CH₂ --, --NH--, ##STR19## --SO₂ --, --SO-- or --S--. Morepreferably R₈ is R₈ " where R₈ " is one of the significances of R₇ "except hydrogen and R₉ is R₉ " where R₉ " is --CH₃, --C₂ H₅ or benzyl orboth R₈ " and R₉ " together with the N-atom to which they are attachedform a pyridinium ring, unsubstituted or substituted by one or twomethyl groups, or is a group β defined above.

Preferably R₁₁ is R₁₁ ' where R₁₁ ' is hydrogen, chloro, nitro, methylor methoxy.

Preferably R₁₂ is R₁₂ ' where R₁₂ ' is ##STR20## or hydrogen;

More preferably R₁₂ is R₁₂ " where R₁₂ " is --CO--CH₂ --Z" or ##STR21##where R₁₃ ", R₁₄ " and Z" are defined below. Preferably R₁₃ is R₁₃ 'where R₁₃ ' is chloro, --OH, --NH₂, ##STR22## N,N-di-(C₂₋₄hydroxyalkyl)amino, ##STR23## where R₂₁ is unsubstituted C₁₋₁₂ alkyl; orC₂₋₁₂ alkyl substituted by --OH; C₃₋₁₂ alkyl interrupted by one to threegroups selected from --N(R₇)-- and ##STR24## --NHCOCH₂ --Z; --CH₂CONH--Y₁ --Z, --Y₁ --Z; ##STR25## where Y₁ is a C₁₋₈ alkylene or a C₃₋₈alkenylene group;

Z is --N(R₇)₂ or --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ ;

R₂₃ is halogen, --OH, --NO₂, C₁₋₄ alkyl or C₁₋₄ alkoxy;

R₂₄ is, --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖ or --CO--Y₂ --Z',--NHCO--Y₂ --Z', --CONH--Y₂ --Z', --SO₂ NH--Y₂ --Z', --Y₂ --Z' or--NHNHCOCH₂ --Z',

where Y₂ is C₁₋₈ alkylene.

More preferably R₁₃ is R₁₃ ", where R₁₃ " is ##STR26## where R₂₁ ' is

--(CH₂)₂₋₃ --N(R₇ ")--(CH₂)₂₋₃ --N(R₇ ")R₆ ',

--(CH₂)₂₋₃ --N.sup.⊕ (R₈ ")₂ --(CH₂)₂₋₃ --N.sup.⊕ (R₈ ")₂ R₆ '2A.sup.⊖,

--(CH₂)₂₋₃ --N(R₇ ")--C₂ H₅,

--(CH₂)₂₋₃ --N.sup.⊕ (R₈ ")₂ --C₂ H₅ A.sup.⊖,

--NHCOCH₂ --Z",

--CH₂ --CONH--Y₂ '--Z", ##STR27## where R₆ ' is methyl or ethyl, and

Y₂ ' is C₁₋₄ alkylene.

Preferably Z is Z' where Z' is --N(R₇ ')₂ or --N.sup.⊕ (R₈ ')₂ R₉'A.sup.⊖.

More preferably Z is Z" where Z" is N(R₇ ')₂ or --N.sup.⊕ (R₈ ")₂ R₉"A.sup.⊖.

Preferably R₁₄ is R₁₄ ' where R₁₄ ' is therefore ##STR28## where R₅, andR₂₁ are defined above. More preferably R₁₄ is R₁₄ " where R₁₄ " is --NR₅"R₂₁ ', ##STR29##

Preferably R₁₉ is hydrogen.

Preferably D is D' where D' is ##STR30## where each R₂₆, independently,is hydrogen, halogen, --NO₂, --NH₂, C₁₋₄ alkyl, C₁₋₄ alkoxy, --CN,trifluoromethyl, phenyl, anilino, benzoyl, carbamoyl, phenoxy,halophenoxy, dihalophenoxy, C₁₋₄ alkylsulphonyl, phenylsulphonyl, C₁₋₄alkylsulphonylamino or N,N-di(C₁₋₄ alkyl)-aminosulphonyl;

each R₂₈ independently, is hydrogen, halogen, C₁₋₄ -alkyl or C₁₋₄ alkoxyand

X is any one of X₁ to X₆₄ and X₁₀₀ to X₁₀₈ below: X₁ a direct bond, X₂,linear or branched C₁₋₄ alkylene, ##STR31## each R₄₂ independently ishalogen, C₁₋₄ alkyl or C₁₋₄ alkoxy,

each R₄₃ independently is linear or branched C₁₋₄ alkylene,

each R₄₄ independently is hydrogen or C₁₋₄ alkyl group,

each R_(42a) independently is hydrogen, Cl, --CH₃ or --OCH₃,

each R_(45a) independently is Cl, --NH(CH₂)₂ OH, OCH₃, --OC₂ H₅, --OH,--NH₂, --N(CH₂ --CH₂ OH)₂, ##STR32## each R₄₅ independently, is halogen,--NH--CH₂ --CH₂ --OH, --N(CH₂ --CH₂ --OH)₂, --NH₂, --OH, --NH--(CH₂)₂₋₃N(C₂ H₅)₂, ##STR33## --OCH₃ or --OC₂ H₅ and g is 1, 2, 3 or 4,preferably 2, 3 or 4.

More preferably X, when one of R₂₈ is not hydrogen, is a direct bond,X₂, X₁₄, X₂₁, X₃₂ or X₄₀.

Preferably when any phenyl ring to which X is attached is substituted,the substituent is in an ortho position to the azo radical attached tothe said ring.

Ka is a diazo or coupling component of the pyrazolone, 5 series,5-aminopyrazole series, α- or β-naphthol series, aniline series, phenolseries, α- or β-aminonaphthalene series, aminonaphthol series,acetoacetyl alkyl or arylamide series, barbituric acid or dimedoneseries or diaminopyridine series or is ##STR34##

In the various component series mentioned above the component may besubstituted by such groups as R₁ to R₄₀ hereinbefore or hereinafterdefined.

Preferably Ka is Ka' where Ka' is a group of any one of the formulae (a)to (1) below ##STR35##

More preferably D is D" where D" is ##STR36## where each R₂₈independently is hydrogen, halogen, C₁₋₄ -alkyl or C₁₋₄ alkoxy, X' isdefined above and K_(a) " is defined below.

K_(a) is more preferably K_(a) " where K_(a) " is a group of one of theformulae a₁ to k₁ below: ##STR37## where R₂₉ is a group ##STR38## whereR₄₆ is hydrogen, ##STR39## --NHCO(CH₂)₂₋₃ --Z, --SO₂ NH(CH₂)₂₋₃ --Z or--CO--Y₁ --Z;

each R₄₇ independently is hydrogen, halogen, C₁₋₄ -alkyl, C₁₋₄ alkoxy,--NO₂ or --CN;

R₄₈ is C₁₋₄ alkoxy and

each q, independently, is 0 or 1 and R₁₃ ', R₁₄ ', Y₁ and Z are definedabove,

R₃₂ is C₁₋₄ alkyl or phenyl;

each R₃₃ independently is hydrogen, C₁₋₄ alkyl, --(CH₂)₂₋₃ OCH₃,--(CH₂)₂ OH, --(CH₂)₂₋₃ N(CH₃)₂ or --(CH₂)₂₋₃ N.sup.⊕ (CH₃)₃ A.sup.⊖.R₃₃ is preferably R₃₃ ' where R₃₃ ' is hydrogen, --(CH₂)₂ OH, --(CH₂)₃--OCH₃, --(CH₂)₂₋₃ --N(CH₃)₂ or --(CH₂)₂₋₃ N.sup.⊕ (CH₃)₃ A.sup.⊖ ;

R₃₄ is --OH or --NH₂ ;

R₃₅ is C₁₋₄ alkyl, --COOR₆, --CON(R_(5a))₂ or --CONH--Y₁ --Z, whereineach R_(5a) is independently C₁₋₄ alkyl or hydrogen, and R₆ is C₁₋₄alkyl;

R₃₆ is hydrogen, ##STR40## where R₄₉ is hydrogen, --CONH--Y₁ --Z, --SO₂--NH--Y₁ --Z, --NHCO(CH₂)₂₋₃ --Z or ##STR41## each R₅₀ independently ishydrogen, halogen, C₁₋₄ alkoxy, --NO₂ ; --NH₂ or C₁₋₄ alkyl,

R₃₇ is ##STR42## --NHCO(CH₂)₁₋₃ --Z, --SO₂ NH--Y₁ --Z, --CONH--Y₁ --Z,--CONHNH₂, --NH--Y₁ --Z, --CH₂ --Z, ##STR43## or hydrogen; R₃₈ is C₁₋₄alkyl, ##STR44## or --(CH₂)₂ CN; preferably R₃₈ is R₃₈ ' where R₃₈ ' is--CH₃, --C₂ H₅, --(CH₂)₂ CN or benzyl;

R₃₉ is C₁₋₄ alkyl or --(CH₂)_(m) --Z; preferably R₃₉ is R₃₉ ' where R₃₉' is --CH₃, C₂ H₅, or --(CH₂)_(m') --Z,

R₄₀ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy;

m is an integer 1 to 6 and m is preferably m' where m' is an integerfrom 2 to 4;

K_(b) is a component of formula (a), (b) or (d) to (1) of componentK_(a) ' and K_(b) ' is a component (a₁), (b₁) or (d₁) to (k₁),

Preferably R₂₉ is R₂₉ ' where R₂₉ ' is --(CH₂)_(m) '--Z', ##STR45##where R₄₆ ' is hydrogen, ##STR46## --NHCO(CH₂)₂₋₃ --Z' or --SO₂--NH--(CH₂)₂₋₃ --Z';

each R₄₇ ' independently is hydrogen, chlorine, bromine, methyl, ethyl,methoxy, ethoxy, --NO₂ or --CN;

R₄₈ ' is methoxy or ethoxy; and

m' is 2, 3 or 4.

Preferably K₁ is K₁ ' where K₁ ' is a group of the formula ##STR47##where R₆₃ and R₆₄ are later defined or has a significance of K_(a) '(independently of K_(a) ').

More preferably K₁ is K₁ " where K₁ " is a group of the formula##STR48## where R₆₃ ' is later defined and R₁₃ ' and R₁₄ ' are definedabove or has a significance of K_(a) " (independently of K_(a) ").

Most preferably K₁ is K_(a) '" where K_(a) '" is a group of the formula##STR49## where the symbols are defined above except R₆₃ " which isdefined below.

Preferably A₁ or A₁₀ is A₁ ' where A₁ ' is ##STR50## where R₅₁ ishydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy;

R₅₂ is --OH, halogen, --CN, --CONH₂, --NHCOC₁₋₄ alkyl, --NHCONH₂,--COOH, --SO₃ H, hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy;

each R₅₃ independently is hydrogen, halogen, --CN, C₁₋₄ alkyl, C₁₋₄alkoxy, --COOH, --SO₃ H or --OH;

Yo is a direct bond, (CH₂)₁₋₃, --O--, --S--, --SO₂ --, --NH--CO--,--NH--CONH--, --NHCO--(CH₂)₂₋₃ --, --CONH--, --CONH(CH₂)₂₋₃ NHCO--,--O--(CH₂)₂₋₃ --O--, --N═N-- or --CH═CH--CO--CH═CH--.

More preferably A₁ or A₁₀ is A₁ " where A₁ " is ##STR51## where R₅₂ ' ishydrogen, chlorine, --OH, methyl or methoxy;

R₅₃ ' is hydrogen, --Cl, --CH₃, --OH or --OCH₃ ;

Y'o is a direct bond, --NH--CO-- or --NHCONH--.

Preferably in A₁ " the free bonds shown are in a meta or para positionto each other (in the phenyl ring) or to Y_(o) (in the Y_(o) -containinggroup).

In the compounds of formula I preferably 0 to 4 sulpho groups arepresent, more preferably up to 2 sulpho groups are present.

Preferably X_(o) is X_(o) ' where X_(o) ' is --NH--, --NHCONH--,--NHCOCH═CHCONH--, --NHCO(CH₂)₂₋₃ CONH--, ##STR52## where R₁₃ ' isdefined above.

More preferably X_(o) is X_(o) " where X_(o) " is --NH--,--NHCOCH═CHCONH-- or --NHCO(CH₂)₂ CONH--.

Preferably, R₁₇ is R₁₇ ', where R₁₇ ' is hydrogen, ##STR53## --N═N--K₁'; --N═N--A₁ '--N═N--K₁ ' or ##STR54## R₂₀ ' is --NR₅ '--Q₁ --N(R₇ ')₂,--NR₅ '--Q₂ --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖ or ##STR55## and the othersymbols are defined above.

More preferably, R₁₇ is R₁₇ ", where R₁₇ " is hydrogen, ##STR56##--N═N--K₁ ", --N═N--A₁ '--N═N--K₁ " or ##STR57## R₂₀ " is --NR₅ "--Q₁--N(R₇ ")₂, --NR₅ "--Q₂ --N.sup.⊕(R₈ ")₂ R₉ "A.sup.⊖ or ##STR58## andthe other symbols are defined above.

Preferably Q₁ is C₂₋₆ alkylene, more preferably C₂₋₃ alkylene, mostpreferably C₃ alkylene.

Preferably R₃₃ is R₃₃ ' where R₃₃ ' is hydrogen, --(CH₂)₂ OH, --(CH₂)₃OCH₃, --(CH₂)₂₋₃ ═N(CH₃)₂ or --(CH₂)₂₋₃ --N.sup.⊕ (CH₃)₃ A.sup.⊖.

Prefera ly R₃₆ Is R₃₆ ' where R₃₆ ' is hydrogen, ##STR59## where R₄₉ 'is hydrogen, --CO--NH--(CH₂)_(m) '--Z'; --NHCO(CH₂)₂₋₃ --Z' or ##STR60##each R₅₀ ' independently is hydrogen, chlorine, methyl or methoxy.

Preferably R₃₇ is R₃₇ ' where R₃₇ ' is ##STR61##

Further according to the invention there are provided azo compounds, inmetal-free, 1:1 or 1:2 metal complex form, in free acid or acid additionsalt form of formula II ##STR62## in which B₁ is hydrogen, C₁₋₄ alkyl,C₂₋₄ alkyl substituted by hydroxy, C₅₋₆ cycloalkyl unsubstituted orsubstituted by 1 or 2 methyl groups, phenyl(C₁₋₃ alkyl), --A₄ '--N(R₇)₂,--A₄ --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ or --N(R₇)₂, and where the other symbolsare defined above.

Preferred compounds of formula II are of formula IIa in metal-free, 1:1or 1:2 metal complex form ##STR63## where B₁ ' is hydrogen, --CH₃, --C₂H₅, --C₂ H₄ OH, cyclohexyl, benzyl, --(CH₂)₂₋₃ --N(R₇ ")₂ or --(CH₂)₂₋₃--N.sup.⊕ (R₈ ")₂ R₉ "A.sup.⊖, and where the other symbols are definedabove.

Preferred compounds of formula IIa are of formula (IIa') in metal-free,1:1 or 1:2 metal complex form ##STR64## in which B₁ " is hydrogen,--CH₃, --C₂ H₅, benzyl, --(CH₂)₂₋₃ --N(R₇ ")₂ or --(CH₂)₂₋₃ --N.sup.⊕(R₈ ")₂ R₉ "A.sup.⊖, where the symbols are defined above.

Alternatively, preferred compounds of formula II are of formula IIb inmetal-free, 1:1 or 1:2 metal complex form ##STR65## where R_(17a) is--N═N--K₁ ', --N═N--A₁ '--N═N--K₁ ' or ##STR66## where the symbols aredefined above.

Preferred compounds of formula IIb are those in which R_(17a) is R_(17a)' where R_(17a) ' is ##STR67##

Alternatively, preferred compounds of formula (I) are of formula III inmetal-free, 1:1 or 1:2 metal complex form, in free acid or acid additionsalt form ##STR68## where R₁ ' is hydrogen or --N═N--D (more preferably--N═N--D) and the other symbols are as defined above.

Preferred compounds of formula III are of formula IIIa ##STR69## whereR₁ " is hydrogen or --N═N--D' (more preferably --N═N--D') and the othersymbols are defined above. Compounds of formula IIIa are in metal-free,1:1 or 1:2 metal complex form where R₁ " is --N═N--D'.

More preferred compounds of formula III are of formula IIIb ##STR70##where R₁ "' is hydrogen or --N═N--D" and the other symbols are definedabove. Compounds of formula IIIb are in metal-free, 1:1 or 1:2 metalcomplex form when R₁ '" is --N═N--D".

Preferred compounds of formula IIIb are of formula IIIc ##STR71## whereR₁ ^(iv) is hydrogen or --N═N--D'" where D"' is ##STR72## where R₂₆ ' ishydrogen, --NO₂, chloro, methyl, methoxy or chlorophenoxy;

R_(27a) is hydrogen, chloro, methyl or methoxy;

R_(27b) is hydrogen, methyl or methoxy;

each R_(26a) is independently nitro, chloro, methoxy or methyl;

X", when both the substituents R_(27a), and R_(27b) are hydrogen, is X₁,X₅, X₆, X₇, X₁₀, X₁₁, X₁₂, X₁₆, X₁₇, X₂₂, X₂₅, X₂₆, X₂₇, X₃₀, X₃₁, X₄₉,X₅₀, X₅₁, X₅₂, X₅₃, X₅₄, X₅₈, X₅₉, X₆₄, X₇₀₋₉₀, X₁₀₁ where R₄₃=--(CH₂)₁₋₂, X₁₀₃ (where R₄₃ is --(CH₂)₁₋₂ and R₄₅ is NH(CH₂)₂₋₃ --N(C₂H₅)₂), X₁₀₄ (where R₄₄ is hydrogen or g is 2 or 3) and X₁₀₈ (where R₄₃is --(CH₂)₁₋₂ --) and otherwise is X₁, X₄₀, X₇₀, X₇₁, X₈₀, X₈₁, X₈₂ orX₈₅. Compounds of formula IIIc are in metal-free, 1:1 or 1:2 metalcomplex form when R₁ ^(iv) is --N═N--D"'.

Preferably when the phenyl rings to which X is attached are substituted,the substituents selected from chloro, methyl and methoxy are in anortho position to the azo group attached to said rings.

Alternatively preferred compounds of formula I are of formula XIV inmetal-free, 1:1 or 1:2 metal complex form; ##STR73## in which one R₆₀ is--OH and the other R₆₀ is NH₂,

R₆₁ is hydrogen, C₁₋₄ alkoxy or --OH

R₆₂ is hydrogen, chloro, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or --OH,

R₆₃ has a significance of R₆₂ independently of R₆₂,

R₆₄ is hydrogen, ##STR74## --N(CH₃)₂, --N.sup.⊕ (CH₃)₃ A.sup.⊖, --N(C₂H₅)₂, --N.sup.⊕ (C₂ H₅)₃ A.sup.⊖, --CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂--Z, --NH--CO--Y₂ --Z, --SO₂ --NH--Y₂ --Z or --NHNHCOCH₂ --Z,

M is hydrogen or a non-chromophoric cation,

and the other symbols are defined above,

with the provisos that

(i) the number of cationic and protonatable basic groups exceeds thenumber of sulpho groups present by at least one;

(ii) R₆₄ is in the 3- or 4-position on the phenyl ring to which it isattached (the positions being as indicated).

Preferred compounds of formula XIV are of formula XIV' in metal-free,1:1 or 1:2 metal complex form; ##STR75## in which R₆₁ ' is hydrogen,methoxy or --OH,

R₆₂ ' is hydrogen, chloro or methyl,

R₆₃ ' is hydrogen, methoxy, --OH, methyl or chloro, and the othersymbols are as defined above,

with the provisos that

(i) the number of cationic and protonable basic groups present exceedsthe number of sulpho groups present by at least one;

(ii) the amino group on ring E is in the 3- or 4-position.

More preferred compounds of formula XIV are of formula XIV" inmetal-free, 1:1 or 1:2 metal complex form ##STR76## in which R₆₃ " ishydrogen, --OH or methoxy, and the other symbols are as defined abovewith the provisos that

(i) the number of cationic and protonable basic groups exceeds thenumber of sulpho groups present by at least one;

(ii) that the amino group on ring E is in the 3- or 4-position (thepositions being as indicated);

(iii) the azo group on ring G is in the 3- or 4-position (the positionsbeing as indicated).

Preferred metallisable groups are --NH₂, --OH or --O(C₁₋₄ alkyl) whichare situated ortho to an azo bridge on a benzo or a phenyl group.Metallisation of such groups can be represented as follows: ##STR77## inwhich each A₅ independently, is --O-- or --NH--

Me_(a) is a 1:1 or 1:2 metal complex forming metal, and both R₆₆ 's andR₆₇ 's are ortho to each other and together form an aromatic ring system(for example together with the two carbon atoms to which they areattached form a ##STR78## group).

Preferred compounds of formula I when in metallised form are of formulaeIVa to IVi: ##STR79## where Y_(a) is --O-- or --NH--

Me is copper, chromium, cobalt, nickel, iron, manganese or zinc for 1:1metal complexes (Me is preferably copper in this case) or Me ischromium, cobalt, iron or nickel for 1:2 metal complexes (Me ispreferably iron in this case);

with the provisos that

(i) in the compounds of formulae IVg, IVh and IVi R₆₄ is in the 3- or4-position, the naphthyl azo group on ring G is in the 3- or 4-positionand the number of cationic and protonable basic groups present exceedsthe number of sulpho groups present;

(ii) in the compounds of formula IVh the group --O--Me--O-- is ortho tothe naphthyl azo group; and

(iii) in the compounds of formulae IVh and IVi when Y_(a) is --NH-- thenR₆₀ is --OH, and when Y_(a) is --O-- then R₆₀ is --NH₂.

The entire specification of parent application Ser. No. 06/485,212,filed Apr. 15, 1982 (including claims) is thereby incorporated byreference in its entirety.

Compounds of formula I where R₁ is hydrogen may be prepared by reactinga compound of formula V ##STR80## with a compound of formula V_(a)##STR81## where R_(60a) is halogen and R_(61a) is hydrogen or a group ofthe formula ##STR82## or by reacting a compound of formula V whereR_(61a) is ##STR83## with a compound of formula VI or VII

    NH(R.sub.7).sub.2                                          (VI)

    N(R.sub.8).sub.2 R.sub.9                                   (VII)

Compounds of formula V can be prepared by known methods, for examplewhere R_(61a) is ##STR84## the compound of formula IV can be prepared byreacting a compound of formula VIII ##STR85## where R_(63a) is ##STR86##with a compound of formula IX ##STR87## to form a compound of formula X##STR88## followed by reduction of the nitro group to an amino group orwhere R_(61a) is hydrogen by saponification of the compound of formulaX.

Compounds of formula I where R₁ is ##STR89## can be prepared by couplingto a diazotised compound of formula XI ##STR90## a compound of formulaXIII ##STR91## by known methods.

Compounds of formula I where R₁ is other than hydrogen can be preparedby reacting a diazotised compound of formula XIa or XIIa ##STR92##

    NH.sub.2 --K                                               XIIa

with a compound of formula XIIIa ##STR93## according to known methods.

Compounds of formula XIV in metal-free form may be prepared by eitherreacting a diazotised compound of formula XV ##STR94## with a compoundof the formula XVI ##STR95## in acid medium to form a compound offormula XVII ##STR96## followed by reacting the compound of formula XVIIwith a diazotised compound of formula XVIII ##STR97## in alkali medium;or by reacting a diazotised compound of formula XVIII with the compoundof formula XVI to form a compound of formula XIX ##STR98## in acidmedium followed by reacting the compound of formula XIX with adiazotised compound of formula XV in alkali medium. The SO₃ H groups canbe converted to the salt form by known methods

Coupling to form compounds of formula I where R₁ is other than hydrogencan be carried out according to known methods. Advantageously, couplingis carried out in aqueous (acid, neutral or alkali) medium at atemperature from -10° C. to room temperature, if necessary in thepresence of a coupling accelerator such as pyridine or urea.Alternatively, coupling may be effected in a mixture of solvents, forexample, water and an organic solvent.

Metallisation of the compounds of formula I when R₁ is other thanhydrogen can be achieved by known methods.

The azo compounds of formula I in 1:1 metal complex form may be preparedby metallising compounds of formula I in metal-free form with a metalselected from copper, cobalt, iron, nickel, manganese, chromium andzinc.

The azo compounds of formula I in 1:2 metal complex form may be preparedby metallising compounds of formula I in metal-free form with a metalselected from chromium, nickel, cobalt and iron.

A further method for the preparation of an azo compound of formula I in1:2 metal complex form is by reacting an azo compound of formula I inmetal-free form with an azo compound 1:1 metal complex when the metal ischromium, nickel, cobalt or iron.

The metallisation process to form a 1:1 metal complex is advantageouslycarried out by treating 1 mole of azo compound with a metallising agentcontaining 1 equivalent of metal.

Metallisation is carried out advantageously in aqueous medium or amixture of water and a water-miscible organic solvent, for exampleacetone, lower alkyl alcohols, dimethylformamide, formamide, glycols oracetic acid at a pH range from 1.0 to 8.0, preferably pH 2 to 7. Themetallisation process may be carried out at a temperature from roomtemperature to the boiling point of the reaction medium.

Alternatively, metallisation may be effected in a wholly organic medium(for example dimethylformamide). Advantageously, for instance,cobaltisation may be carried out in the presence of an inorganic nitritesuch as lithium, sodium, ammonium or potassium nitrite in the ratio of 2to 6 moles of nitrite per gram atom of cobalt.

Suitable cobalt-yielding compounds are, for example, cobalt (II) and Co(III) sulphate, acetate, formate and chloride.

Copper-yielding compounds are, for example cupric sulphate, cupricformate, cupric acetate and cupric chloride.

The nickel-yielding compounds are Ni (II) and Ni (III) compounds, suchas nickel formate, nickel acetate and nickel sulphate.

Preferred manganese-yielding compounds are Mn (II) compounds andiron-yielding compounds are Fe (II) and Fe (III) compounds. Examples ofthese and zinc-yielding compounds are manganese, iron and zinc formate,acetate and sulphate.

Preferred chromium-yielding compounds are Cr (II) and Cr (III) formate,acetate and sulphate.

In the compounds of formula I the anions A.sup.⊖ can be anynon-chromophoric anions such as those conventional in basic dyestuffchemistry. Suitable anions include chloride, bromide, sulphate,bisulphate, methylsulphate, aminosulphonate, perchlorate,benzenesulphonate, oxalate, maleate, acetate, propionate, lactate,succinate, tartrate, malate, methanesulphonate and benzoate, as well ascomplex anions, for example, zinc chloride double salts and anions ofboric acid, citric acid, glycollic acid, diglycollic acid and adipicacid or addition products of orthoboric acid with polyalcohols with atleast one cis diol group present. These anions can be exchanged for eachother by ion exchange resins or by reaction with acids or salts, forexample via the hydroxide or bicarbonate or according to GermanOffenlegungsschrift No. 2,001,748 or 2,001,816.

The azo compounds of formula I are suitably worked up into solid orliquid preparations, for example by granulation or by dissolving in asuitable solvent. The compounds of formula I are suitable for dyeing,padding or printing on fibres, threads or textile materials particularlynatural or regenerated cellulose materials for example cotton, orsynthetic polyamides or synthetic polyesters in which the acid groupshave been modified. Such a polyamide is described in Belgian Pat. No.706,104 and such a synthetic polyester is described in U.S. Pat. No.3,379,723.

The azo compounds of formula I may also be applied to bast fibres suchas hemp, flax, sisal, jute, coir or straw.

The azo compounds of formula I are also used for dyeing, padding orprinting fibres, threads or textiles produced therefrom which consist ofor contain homo- or mixed polymers of acrylonitrile or of1,1-dicyanoethylene.

The textile material is dyed, printed or pad-dyed in accordance withknown methods. Acid modified-polyamide is dyed particularlyadvantageously in an aqueous, neutral or acid medium, at temperatures of60° C. to boiling point or at temperatures above 100° C. under pressure.

The textile material may also be dyed by the compounds of formula I inorganic solvents, e.g. in accordance with the directions given in GermanOffenlegungschrift No. 2,437,549.

Cellulose material is mainly dyed by the exhaust process i.e. from along or short bath, at room temperature to boiling temperature,optionally under pressure, whereby the ratio of the bath is from 1:1 to1:100 and preferably from 1:20 to 1:50. If dyeing is effected from ashort bath, then the liquor ratio is 1:5 to 1:15. The pH of the dyebathvaries between 3 and 10 (for short and long dyebaths). Dyeing preferablytakes place in the presence of electrolytes.

Printing may be effected by impregnation with a printing paste producedby known methods.

The dyes of formula I are also suitable for dyeing or printing paper,e.g. for the production of bulk-dyed, sized and unsized paper. Thedyestuffs may similarly be used for dyeing paper by the dipping process.The dyeing of paper is effected by known methods.

The dyes of formula I are also suitable for dyeing or printing leatherby known methods.

Dyeings with good fastness are obtained on both paper and leather.

Dyeings made with the dyes of formula I on leather have good lightfastness properties, good diffusion properties with PVC, good water-,wash and sweat-fastness properties, good fastness to dry cleaning, goodfastness to drops of water and good fastness to hard water.

Dyeings prepared with dyes of formula I (where R₁ is other thanhydrogen) on paper produce a substantially clear spent liquor which isimportant for environmental reasons. The dyes of formula I have goodbuild-up properties, do not run once applied to paper and are not pHsensitive. Dyeings produced with dyes of formula I have good lightfastness and the nuance on exposure for a long time to light fades tonein tone. The dyes of formula I have good wet-fastness properties notonly for water but also for milk, soap, water, sodium chloride solution,fruit juice, and sweetened mineral water. Further dyeings made with dyesof formula I are fast for alcoholic beverages due to a good alcoholfastness. Further the dyes of formula I have good nuance stability.

The dyes of formula I may be converted into dyeing preparations.Processing into stable liquid or solid dyeing preparations may takeplace in a generally known manner, advantageously by grinding orgranulating or by dissolving in suitable solvents, optionally adding anassistant, e.g. a stabiliser or dissolving intermediary such as urea.Such preparations may be obtained, for example, as described in FrenchPatent Specification Nos. 1,572,030 and 1,581,900 or in accordance withGerman DOS Nos. 2,001,748 and 2,001,816.

Liquid preparations of the compounds of formula I preferably comprise 10to 30% by weight of a compound of formula I and to 30% of a solubilisingagent such as urea, lactic acid or acetic acid, the rest of thecomposition being water. Solid preparations preferably comprise 20 to80% dyestuff, 20 to 80% solubilising agent such as urea or Na₂ SO₄ and 2to 5% water.

In the following Examples all parts and percentages given are by weightand the temperatures given are in degree Centigrade, unless indicated tothe contrary.

EXAMPLE 1

390 Parts (2 moles) of para-nitrobenzoic acid ethyl ester are warmed in3200 parts of ethanol and 360 parts (6 moles) of ethylene diamine at60°-65°. After stirring for several hours a fine crystalline productresults which after filtration produces 360 parts of a compound offormula (1a) ##STR99## having a melting point (of the unpurifiedproduct) of 132°-134°.

A compound of formula (1b) ##STR100## is formed by reacting the compoundof formula (1a) with the product of slight excess pyridine and 1 mole ofchloroacetic acid methyl ester, in ethanol at 55° C.

Without isolating the compound (1b) 1 mole of acetoacetic acid methylester is added to the reaction mixture and this is treated at 25° C. inthe presence of base by known methods to produce a compound of formula(1c) ##STR101## which can be reduced by the Bechamps method to thecorresponding amine.

After adding water to the reaction mixture, the compound of formula (1c)precipitates out.

The compound of formula (1c) is saponified in 5-7% hydrochloric acidaccording to known methods to form an amine of formula (1d) ##STR102##

The compound of formula (Id) is reacted according to known methods inwater at about 90° and a pH of 9 with a compound of formula (Ie)##STR103##

to form a compound of formula (If) ##STR104## The compound of formula(If) is very water soluble, particularly in acid medium and can be usedas a coupling component in the preparation of azo dyestuffs.

EXAMPLE 2

In a similar manner to the method of Example 1, a compound of theformula ##STR105## is formed using 1,3-diaminopropane instead ofethylene diamine and chloroacetyl chloride and trimethylamine instead ofthe compound of formula (1e).

EXAMPLE 3

225 Parts (1.5 moles) of m-aminoacetanilide in the form of the acidaddition salt are placed in a mixture of equivoluminar glacial aceticacid and water together with sodium acetate. On cooling to 0°-5° C., 254parts of chloroacetyl chloride (2.25 moles) are added over 2 hours. Aproduct of formula 3a ##STR106## is formed. 1 mole of the compound offormula 3a is reacted according to known methods with 1 mole of pyridineto form a compound of formula 3b ##STR107## Without the need to isolatethe compound of formula 3b 1 mole of acetoacetic acid methyl ester isadded to the reaction mixture and according to known methods at roomtemperature in the presence of base a compound of formula 3c ##STR108##is formed.

At 95°-98° C. the compound of formula 3c is saponified with about 5%hydrochloric acid to form a compound of formula 3d ##STR109##

The compound of formula 3d is converted into that of formula 3e##STR110## in a similar way to that described in Example 1.

EXAMPLES 4 TO 12

Compounds of the formula ##STR111## where R is defined in Table 1 below,may be prepared by a method analogous to that of Example 1.

                                      TABLE 1                                     __________________________________________________________________________    Example                                                                       No.  R                                                                        __________________________________________________________________________          ##STR112##                                                              5                                                                                   ##STR113##                                                              6                                                                                   ##STR114##                                                              7                                                                                   ##STR115##                                                              8                                                                                   ##STR116##                                                              9                                                                                   ##STR117##                                                              10                                                                                  ##STR118##                                                              11                                                                                  ##STR119##                                                              12                                                                                  ##STR120##                                                              __________________________________________________________________________

EXAMPLES 13 TO 44

In the following Examples compounds of the formula ##STR121## where T, Aand R₂ are given in Table 2 below, may be prepared by a method analogousto Example 1. In Table 2, T₂ to T₇ and A₂ to A₃₂ are as given below andA.sup.⊖ is CH₃ COO.sup.⊖ ; ##STR122##

                  TABLE 2                                                         ______________________________________                                        Example                                                                       No.       T     A                    R.sub.2                                  ______________________________________                                        13        H     C.sub.2 H.sub.4      H                                        14        T.sub.2                                                                             "                    A.sub.2                                  15        T.sub.3                                                                             "                    A.sub.3                                  16        T.sub.4                                                                             "                    A.sub.4                                  17        T.sub.6                                                                             "                    A.sub.5                                  18        T.sub.7                                                                             "                    A.sub.6                                  19        T.sub.4                                                                                                  A.sub.7                                  20        "     "                    A.sub.8                                  21        T.sub.5                                                                             "                    A.sub.9                                  22        T.sub.4                                                                              ##STR123##          A.sub.10                                 23        "     CH.sub.2CHCHCH.sub.2 A.sub.11                                 24        T.sub.2                                                                             "                    A.sub.12                                 25        T.sub.4                                                                             C.sub.2 H.sub.4      A.sub.13                                 26        "     "                    A.sub.14                                 27        "     "                    A.sub.15                                 28        "     "                    A.sub.16                                 29        "     "                    A.sub.17                                 30        "     "                    A.sub.18                                 31        "     "                    A.sub.19                                 32        "     "                    A.sub.20                                 33        "     "                    A.sub.21                                 34        "     "                    A.sub.22                                 35        "     "                    A.sub.23                                 36        "     "                    A.sub.24                                 37        "     "                    A.sub.25                                 38        "     "                    A.sub.26                                 39        "     "                    A.sub.27                                 40        "     "                    A.sub.28                                 41        "     "                    A.sub.29                                 42        "     "                    A.sub.30                                 43        "     "                    A.sub.31                                 44        "     "                    A.sub.32                                 ______________________________________                                    

EXAMPLE 45

A compound of the formula 45a ##STR124## is prepared by diazotising 1mole of 4-aminoacetanilide and coupling with 1 mole of the compound Ifof Example 1.

By the additions of 30% hydrochloric acid to the aqueous solution ofcompound 45a, a 7% hydrochloric acid containing solution is produced andthis is refluxed for 10 hours. A compound of the formula 45b results##STR125## 1 mole of the compound 45b is then diazotised and then iscoupled to 1 mole of a compound of the formula 45c ##STR126## to form acompound of formula 45d ##STR127## and this compound dyes paper a blueviolet tone.

A similar product can be obtained by using 1 mole of a compound offormula 45e ##STR128## instead of the compound of formula 45c

EXAMPLE 46

6.9 Parts of 1-amino-4-nitrobenzene (1/20 mole) is diazotised inhydrochloric acid solution at -0° to 5° C. with 3.5 parts (1/20 mole)sodium nitrite. Then 1/40 mole of the diazonium solution is coupled to 8parts of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid (1/40 mole)pH at 1. The remaining 1/40 mole diazonium solution is coupled at pH 9to the monoazo dyestuff so formed to form a compound of formula 46a##STR129##

The nitro groups of the compound 45a are reduced according to knownmethods, then both --NH₂ groups so formed are diazotised and then 1 moleof the diazotised compound is coupled to 2 moles the compound Ie ofExample 1 to form a compound of formula 46b. ##STR130##

The compound 46b dyes paper a black tone.

EXAMPLES 47 TO 64

Compounds of the formula ##STR131## in which the symbols are defined inTable 3 below (where symbols T₄₋₇ and A₂₋₄ are defined under Examples 13to 44 and the symbols B₂ -B₁₁ are defined below) can be made in ananalogous manner to the method of Example 46. ##STR132##

                                      TABLE 3                                     __________________________________________________________________________    EX.                                                                           No.                                                                              T.sub.a                                                                         R.sub.2                                                                         T.sub.b                                                                         B K.sub.1 K.sub.3 K.sub.2                                            __________________________________________________________________________    47 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                                  ##STR133##                                                                            ##STR134##                                        48 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                         "       "       "                                                  49 T.sub.4                                                                         H T.sub.5                                                                         B.sub.4                                                                         "                                                                                      ##STR135##                                                                           "                                                  50 T.sub.4                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.4                                                                          ##STR136##                                                                            ##STR137##                                                                           "                                                  51 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                          ##STR138##                                                                            ##STR139##                                                                           "                                                  52 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                         "                                                                                      ##STR140##                                                                           "                                                  53 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                         "       "       "                                                  54 T.sub.5                                                                         A.sub.2                                                                         T.sub.6                                                                         B.sub.8                                                                         "                                                                                      ##STR141##                                                                            ##STR142##                                        55 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                         "       "       "                                                  56 T.sub.7                                                                         A.sub.4                                                                         T.sub.5                                                                         B.sub.8                                                                          ##STR143##                                                                           "       "                                                  57 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                          ##STR144##                                                                            ##STR145##                                                                           "                                                  58 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.8                                                                         "       "       "                                                  59 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                         "                                                                                      ##STR146##                                                                            ##STR147##                                        60 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                         "       "       "                                                  61 T.sub.4                                                                         A.sub.2                                                                         T.sub.7                                                                         B.sub.2                                                                         "                                                                                      ##STR148##                                                                           "                                                  62 T.sub.5                                                                         A.sub.2                                                                         T.sub.4                                                                         H "       "       "                                                  63 T.sub.4                                                                         A.sub.2                                                                         T.sub.4                                                                         B.sub.4                                                                         "                                                                                      ##STR149##                                                                           "                                                  64 T.sub.5                                                                         A.sub.2                                                                         T.sub.5                                                                         B.sub.8                                                                         "       "       "                                                  __________________________________________________________________________

The compounds of Examples 47 to 64 dye paper a black tone.

EXAMPLE 65

1/20 mol of para nitroaniline is diazotised and coupled to 1/20 mol of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid. To the resultingmonoazo dyestuff, 1/20 mol of diazotised1-amino-2-hydroxy-4-nitrobenzene is coupled to give a compound offormula 65a ##STR150##

The nitro groups of the compound 65a are reduced with sodium sulphide atpH 11-12. The diamino diazo compound so formed is tetrazotised as inExample 46 and coupled to 1/10 mol of the compound of Ie of Example 1 toform a compound of formula 65b ##STR151##

This dyestuff dyes paper a black shade.

This compound may also be metallised with copper, iron, chromium orcobalt to form a 1:1 metal complex or with chromium, cobalt or iron toform a 1:2 metal complex according to known methods.

EXAMPLES 66 TO 68

The following compounds can be made by a method analogous to that ofExample 65 (or by other known methods) from the corresponding startingcompounds.

EXAMPLE 66 ##STR152## EXAMPLES 67 AND 68

In these Examples the group R_(a) is of the formula ##STR153##

A compound of the formula ##STR154## where R₂ is A₂ (defined underExamples 13 to 44) may be prepared by an analogous method to that ofExample 46 or by any other known method.

A compound of the formula ##STR155## where R₂ is A₂ (defined underExamples 13 to 44) may be prepared by an analogous method to that ofExample 46 (or by any other known method).

In Examples 67 and 68 R₂ may be replaced by hydrogen or any of thegroups A₃ to A₃₂ defined under Examples 13 to 46.

These dyestuffs dye paper a blue tone.

EXAMPLES 69 AND 70

In these Examples R_(b) is a group of the formula ##STR156##

A compound of the formula of Example 67 in which R_(a) is replaced byR_(b) (Example 69) can be prepared by an analogous method to that ofExample 67.

A compound of the formula of Example 68 in which R_(a) is replaced byR_(b) (Example 70) may be prepared by an analogous method to that ofExample 68.

In Examples 69 and 70, R₂ may be replaced by hydrogen or any other groupA₃ -A₃₂ defined under Examples 13 to 44. The dyeings produced fromcompounds of Examples 69 and 70 are of a blue tone.

EXAMPLE 71

From the corresponding starting compounds, a compound of the formula 71a##STR157## can be prepared by a method analogous to that of Example 45and from corresponding starting products a compound of formula 71b##STR158## can be prepared by a method analogous to that of Example 45.The compounds of formula 71a and 71b dye paper a blue tone.

EXAMPLE 72

From suitable starting compounds a compound of formula 72a ##STR159## beprepared by a method analogous to that of Example 45.

A compound of formula 72b ##STR160## where R_(c) is ##STR161## may beformed by diazotising the compound of formula 72a and coupling with acompound of the formula H--R_(c)

The compound of formula 72a is violet in colour and the compound offormula 72b dyes paper a black tone.

EXAMPLES 73 TO 106

By an analogous method to that of Example 65 (or by any other knownmethod) compounds of the formula ##STR162## are produced in which thesymbols are defined in the Table 4 below and T₂₋₄ are defined underExamples 13 to 44 and B₄₋₈ are defined under Examples 47 to 64 and B₁₂is ##STR163##

                  TABLE 4                                                         ______________________________________                                                         position                                                                      of     position of                                                            floating                                                                             floating gp.                                          EX.              group in                                                                             in naphtha-                                           No.  T     T.sub.1                                                                             ring A lene ring                                                                             B.sub.1     B                                 ______________________________________                                        73   T.sub.4                                                                             T.sub.4                                                                             4'     3       --(CH.sub.2).sub.3 --N(CH.sub.3).sub.2                                                    B.sub.4                           74   T.sub.4                                                                             T.sub.4                                                                             3'     2       "           B.sub.4                           75   T.sub.4                                                                             T.sub.4                                                                             3'     3       "           B.sub.4                           76   T.sub.4                                                                             T.sub.4                                                                             4'     3       "           H                                 77   T.sub.4                                                                             T.sub.2                                                                             4'     3       "           B.sub.4                           78   T.sub.4                                                                             T.sub.2                                                                             4'     2       "           B.sub.4                           79   T.sub.4                                                                             T.sub.2                                                                             4'     2       "           B.sub.4                           80   T.sub.4                                                                             T.sub.2                                                                             3'     2       "           B.sub.4                           81   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     B.sub.8                           82   T.sub.4                                                                             T.sub.4                                                                             3'     2       B.sub.8     B.sub.8                           83   T.sub.4                                                                             T.sub.4                                                                             3'     3       B.sub.8     B.sub.8                           84   T.sub.4                                                                             T.sub.4                                                                             4'     3       B.sub.8     B.sub.8                           85   T.sub.4                                                                             T.sub.4                                                                             4'     3       B.sub.8     H                                 86   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     H                                 87   T.sub.4                                                                             T.sub.4                                                                             3'     3       B.sub.8     H                                 88   T.sub.4                                                                             T.sub.4                                                                             3'     2       B.sub.8     H                                 89   T.sub.4                                                                             T.sub.4                                                                             4'     3       B.sub.8     B.sub.4                           90   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     B.sub.4                           91   T.sub.4                                                                             T.sub.4                                                                             3'     3       B.sub.8     B.sub.4                           92   T.sub.4                                                                             T.sub.4                                                                             3'     2       B.sub.8     B.sub.4                           93   T.sub.4                                                                             T.sub.2                                                                             4'     3       B.sub.8     B.sub.4                           94   T.sub.4                                                                             T.sub.2                                                                             4'     2       B.sub.8     B.sub.4                           95   T.sub.4                                                                             T.sub.2                                                                             3'     3       B.sub.8     B.sub.4                           96   T.sub.4                                                                             T.sub.2                                                                             3'     2       B.sub.8     B.sub.4                           97   T.sub.2                                                                             T.sub.4                                                                             4'     3       B.sub.4     B.sub.4                           98   T.sub.2                                                                             T.sub.4                                                                             4'     2       B.sub.4     B.sub.8                           99   T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.4     B.sub.8                           100  T.sub.4                                                                             T.sub.4                                                                             4'     3       H           B.sub.8                           101  T.sub.4                                                                             T.sub. 4                                                                            4'     2       H           B.sub.8                           102  T.sub.4                                                                             T.sub.4                                                                             4'     2       .sub. B.sub.12                                                                            B.sub.8                           103  T.sub.4                                                                             T.sub.4                                                                             4'     3       "           H                                 104  T.sub.4                                                                             T.sub.4                                                                             4'     2       "           B.sub.4                           105  T.sub.4                                                                             T.sub.4                                                                             4'     3       "           .sub. B.sub.12                    106  T.sub.4                                                                             T.sub.4                                                                             4'     2       B.sub.8     .sub. B.sub.12                    ______________________________________                                    

The compounds of Examples 73 to 106 may also contain OH groups inpositions 2', 3' or 4'. In these cases these compounds can be metallisedto form 1:1 metal complexes with copper, chromium, cobalt or iron or 1:2metal complexes with chromium, cobalt or iron.

Compounds of Examples 73-106 may also contain OCH₃ groups in positions2', 3' or 4'. In these cases these compounds may be metallised to form1:1 metal complexes, preferably with copper.

The compounds so formed are of the formula ##STR164## or of the formula##STR165## where Me is copper, chromium, cobalt or iron (to form 1:1metal complexes) or chromium, cobalt or iron (to form 1:2 metalcomplexes).

EXAMPLE 107

12.3 Parts of ortho anisidine (0.1 mole) are diazotised and then coupledto a compound of formula (107a) ##STR166## to form a compound of theformula 107b ##STR167##

This dyestuff dyes paper a yellow shade. The dyestuff (107b) can be usedfor dyeing polyacrylonitrile in the mass.

EXAMPLES 108 TO 131

Compounds of the formula ##STR168## in which T, R₂, R_(a) and R_(b) aredefined in Table 5 below and significances T₂₋₇ and A₂₋₄ are definedunder Examples 13 to 44, can be prepared by a method analogous to thatof Example 107.

    ______________________________________                                                                         Significance of R.sub.b and                  Ex.                Significance of R.sub.a and                                                                 position in                                  No.  T      R.sub.2                                                                              position in phenyl ring                                                                     phenyl ring                                  ______________________________________                                        108  H      A.sub.2                                                                              H             H                                            109  T.sub.2                                                                              A.sub.3                                                                              3-Cl          H                                            110  T.sub.3                                                                              A.sub.2                                                                              4-Cl          H                                            111  T.sub.4                                                                              H      H             H                                            112  T.sub.4                                                                              H      2-NO.sub.2    H                                            113  T.sub.4                                                                              H      2-NO.sub.2    4-Cl                                         114  T.sub.4                                                                              A.sub.2                                                                              H             H                                            115  T.sub.4                                                                              A.sub.2                                                                              2-NO.sub.2    H                                            116  T.sub.4                                                                              A.sub.2                                                                              2-Cl          4-NO.sub.2                                   117  T.sub.4                                                                              A.sub.2                                                                               ##STR169##   H                                            118  T.sub.4                                                                              A.sub.3                                                                              H             H                                            119  T.sub.4                                                                              A.sub.4                                                                              2-NO.sub.2    4-Cl                                         120  T.sub.4                                                                              A.sub.4                                                                              4-OCH.sub.3   H                                            121  T.sub.5                                                                              H      H             H                                            122  T.sub.5                                                                              A.sub.2                                                                              4-NO.sub.2    H                                            123  T.sub.5                                                                              A.sub.2                                                                              2-Cl          4-NO.sub.2                                   124  T.sub.5                                                                              A.sub.4                                                                               ##STR170##   H                                            125  T.sub.6                                                                              H       H            H                                            126  T.sub.6                                                                              A.sub.2                                                                              4-NO.sub.2    H                                            127  T.sub.6                                                                              A.sub.4                                                                              2-Cl          4-NO.sub.2                                   128  T.sub.7                                                                              A.sub.2                                                                              2-NO.sub.2    4-Cl                                         129  T.sub.7                                                                              A.sub.4                                                                               ##STR171##   H                                            130  T.sub.4                                                                              A.sub.2                                                                              2-OCH.sub.3   5-CH.sub.3                                   131  T.sub.5                                                                              A.sub.4                                                                              2-OCH.sub.3   5-OCH.sub.3                                  132  T.sub.4                                                                              A.sub.4                                                                              2-CH.sub.3    3-CH.sub.3                                   ______________________________________                                    

The dyestuffs of Examples 108 to 132 produce dyeings of a yellow tone.These dyestuffs are also useful for dyeing polyacrylonitrile in themass.

EXAMPLE 133

Using suitable starting compounds, a compound of formula 133a ##STR172##may be prepared using an analogous method to Example 107.

Dyeings so produced are of a gold-yellow tone.

EXAMPLES 134 TO 139

Compounds of the formula ##STR173## in which the symbols are given inTable 6 below may be prepared by known methods from suitable startingcompounds.

                  TABLE 6                                                         ______________________________________                                        EX.                                                                           No.  T      R.sub.2                                                                              R.sub.a R.sub.b R.sub.s R.sub.t                            ______________________________________                                        134  T.sub.5                                                                              A.sub.2                                                                              --OCH.sub.3                                                                           --CH.sub.3                                                                            4-CH.sub.3                                                                            H                                  135  T.sub.7                                                                              A.sub.2                                                                              "       --OCH.sub.3                                                                           2-OCH.sub.3                                                                           H                                  136  T.sub.4                                                                              A.sub.4                                                                              "       "       2-CH.sub.3                                                                            5-CH.sub.3                         137  T.sub.6                                                                              A.sub.2                                                                              "       --CH.sub.3                                                                            4-C.sub.4 H.sub.9                                                                     H                                  138  T.sub.5                                                                              A.sub.4                                                                              "       --OCH.sub.3                                                                           2-OCH.sub.3                                                                           5-CH.sub.3                         139  T.sub.4                                                                              A.sub.2                                                                              --CH.sub.3                                                                            --OCH.sub.3                                                                           2-OCH.sub.3                                                                           H                                  ______________________________________                                    

The compounds of Examples 134 to 139 produce dyeings of gold-yellow toorange tones and have good fastness properties.

EXAMPLES 140 TO 162

Compounds of the formula ##STR174## in which the symbols are defined inTable 7 below (symbols T₂₋₇ and A₂₋₄ are defined under Examples 13 to 44and symbols B₂₋₁₁ are defined under Examples 47 to 64) may be made byanalogous methods to that of Example 107 from suitable startingcompounds.

                  TABLE 7                                                         ______________________________________                                                                position of                                           EX.                     floating                                              No.      T     R.sub.2  azo group                                                                             T.sub.1 B                                     ______________________________________                                        140      T.sub.4                                                                             A.sub.2  4       T.sub.4 B.sub.6                               141      H     A.sub.2  4       H       H                                     142      T.sub.2                                                                             A.sub.2  4       T.sub.3 B.sub.2                               143      T.sub.3                                                                             A.sub.4  4       T.sub.4 B.sub.3                               144      T.sub.4                                                                             H        4       H       B.sub.4                               145      T.sub.5                                                                             H        4       H       B.sub.5                               146      H     A.sub.2  4       T.sub.4 B.sub.6                               147      T.sub.6                                                                             A.sub.2  4       T.sub.2 B.sub.7                               148      T.sub.7                                                                             A.sub.2  4       H       B.sub.8                               149      H     H        4       T.sub.4 B.sub.9                               150      H     A.sub.2  4       H       B.sub.8                               151      H     A.sub.4  4       H       B.sub.9                               152      T.sub.4                                                                             H        3       T.sub.4 B.sub.6                               153      T.sub.5                                                                             H        3       T.sub.5 B.sub.6                               154      T.sub.4                                                                             H        4       T.sub.4 B.sub.6                               155      T.sub.5                                                                             H        3       T.sub.5 B.sub.6                               156      T.sub.4                                                                             A.sub.2  3       T.sub.5 H                                     157      T.sub.5                                                                             A.sub.4  3       T.sub.6 H                                     158      T.sub.3                                                                             A.sub.2  3       T.sub.5 B.sub.2                               159      T.sub.4                                                                             H        4       T.sub.4 .sub. B.sub.10                        160      T.sub.5                                                                             A.sub.2  3       T.sub.4 .sub. B.sub.10                        161      T.sub.5                                                                             A.sub.2  4       T.sub.4 .sub. B.sub.11                        162      T.sub.4                                                                             H        3       T.sub.4 .sub. B.sub.11                        ______________________________________                                    

Compounds of Examples 140, to 151, 154, 159 and 162 produce dyeings ofdyeings of a violet tone whereas the compounds of Examples 152, 153, 155to 158, 160 and 161 produce dyeings of a reddish yellow to orange tone.

EXAMPLES 163 TO 186

Compounds of the formula ##STR175## in which the symbols are defined inTable 8 below, may be prepared by an analogous method to that of Example107. Symbols T₂₋₄ and A₂₋₄ are defined under Examples 13 to 44 andsymbols K₁₋₁₇ are given below.

Compounds of Examples 163 to 168, 179 and 185 produce dyeings of a redshade, of Examples 169 to 175, 183 and 184 a yellow tone, of Examples176 to 178 a blue tone and of Examples 180 to 182 and 186 an orangetone. ##STR176##

                  TABLE 8                                                         ______________________________________                                        EX.                     Position of floating                                  No.     T     R.sub.2   azo group   K                                         ______________________________________                                        163     T.sub.4                                                                             A.sub.2   4-          K.sub.1                                   164     T.sub.5                                                                             A.sub.2   4-          K.sub.2                                   165     T.sub.6                                                                             A.sub.2   4-          K.sub.3                                   166     T.sub.4                                                                             A.sub.4   4-          K.sub.4                                   167     T.sub.5                                                                             A.sub.4   4-          K.sub.5                                   168     T.sub.2                                                                             A.sub.2   4-          K.sub.6                                   169     H     A.sub.2   4-          K.sub.7                                   170     T.sub.4                                                                             A.sub.4   4-          K.sub.8                                   171     H     A.sub.4   4-          K.sub.9                                   172     T.sub.5                                                                             H         4-          K.sub.10                                  173     T.sub.5                                                                             A.sub.4   4-          K.sub.11                                  174     T.sub.6                                                                             A.sub.4   4-          K.sub.12                                  175     T.sub.7                                                                             A.sub.2   4-          K.sub.13                                  176     T.sub.4                                                                             A.sub.2   4-          K.sub.14                                  177     T.sub.4                                                                             A.sub.2   4-          K.sub.15                                  178     T.sub.5                                                                             A.sub.4   4-          K.sub.16                                  179     T.sub.6                                                                             A.sub.2   4-          K.sub.17                                  180     T.sub.5                                                                             A.sub.2   4-          K.sub.18                                  181     T.sub.4                                                                             A.sub.2   3-          K.sub.1                                   182     T.sub.6                                                                             H         3-          K.sub.5                                   183     T.sub.7                                                                             H         3-          K.sub. 8                                  184     T.sub.3                                                                             A.sub.4   3-          K.sub.12                                  185     T.sub.4                                                                             A.sub.2   3-          K.sub.14                                  186     T.sub.5                                                                             H         3-          K.sub.17                                  ______________________________________                                    

EXAMPLES 187 TO 243

According to a method analogous to that of Example 107 compounds offormula ##STR177## in which the symbols are defined in Table 9 below(where the symbols A₂₋₄ and R₂₋₇ are defined under Examples 13 to 44 andthose symbols of X₁₋₁₀₈ used in Table 9 are defined below) can beprepared.

The symbols X₁ to X₁₀₈ used in Table 9 are as follows:

X₁ is a direct bond

X₅ --S--, X₆ --O--, X₇ --CH═CH--, X₁₀ --NH--, X₁₁ --NH--CO--,

X₁₂ ##STR178## X₁₆ ##STR179## X₁₇ --SO₂ --NH--, X₂₂ --CO--NH--NH--CO--,##STR180##

                  TABLE 9                                                         ______________________________________                                        EX.                                                                           No.  T     R.sub.2                                                                             X                                                            ______________________________________                                        187  H     A.sub.2                                                                             X.sub.1                                                      188  T.sub.2                                                                             A.sub.2                                                                             X.sub.5                                                      189  T.sub.3                                                                             A.sub.2                                                                             X.sub.6                                                      190  T.sub.4                                                                             A.sub.4                                                                             X.sub.7                                                      191  T.sub.5                                                                             A.sub.4                                                                             X.sub.10                                                     192  T.sub.6                                                                             A.sub.2                                                                             X.sub.11                                                     193  T.sub.7                                                                             A.sub.2                                                                             X.sub.12                                                     194  T.sub.4                                                                             A.sub.2                                                                             X.sub.16                                                     195  H     A.sub.2                                                                             X.sub.17                                                     196  T.sub.4                                                                             A.sub.4                                                                             X.sub.22                                                     197  H     A.sub.2                                                                             X.sub.26                                                     198  T.sub.4                                                                             A.sub.4                                                                             X.sub.27                                                     199  T.sub.5                                                                             H     X.sub.30                                                     200  T.sub.6                                                                             A.sub.2                                                                             X.sub.45                                                     201  T.sub.7                                                                             A.sub.2                                                                             X.sub.49                                                     202  T.sub.4                                                                             A.sub.4                                                                             X.sub.50                                                     203  T.sub.5                                                                             A.sub.2                                                                             X.sub.51                                                     204  T.sub.6                                                                             A.sub.2                                                                             X.sub.52                                                     205  T.sub.7                                                                             A.sub.2                                                                             X.sub.53                                                     206  H     A.sub.2                                                                             X.sub.54                                                     207  T.sub.2                                                                             A.sub.2                                                                             X.sub.58                                                     208  T.sub.4                                                                             A.sub.4                                                                             X.sub.59                                                     209  T.sub.5                                                                             H     X.sub.60                                                     210  T.sub.6                                                                             A.sub.2                                                                             X.sub.61                                                     211  T.sub.7                                                                             A.sub.4                                                                             X.sub.62                                                     212  T.sub.4                                                                             A.sub.2                                                                             X.sub.70                                                     213  H     A.sub.2                                                                             X.sub. 71                                                    214  T.sub.2                                                                             A.sub.2                                                                             X.sub.73                                                     215  T.sub.4                                                                             A.sub.2                                                                             X.sub.74                                                     216  T.sub.5                                                                             A.sub.4                                                                             X.sub.75                                                     217  T.sub.6                                                                             A.sub.2                                                                             X.sub.79                                                     218  T.sub.4                                                                             A.sub.2                                                                             X.sub.80                                                     219  T.sub.5                                                                             A.sub.2                                                                             X.sub.81                                                     220  T.sub.4                                                                             A.sub.2                                                                             X.sub.82                                                     221  T.sub.4                                                                             A.sub.2                                                                             X.sub.85                                                     222  T.sub.5                                                                             A.sub.2                                                                             X.sub.86                                                     223  T.sub.6                                                                             H     X.sub.87                                                     224  T.sub.7                                                                             A.sub.3                                                                             X.sub.88                                                     225  T.sub.2                                                                             A.sub.2                                                                             X.sub.89                                                     226  T.sub.3                                                                             A.sub.4                                                                             X.sub.90                                                     227  T.sub.4                                                                             A.sub.2                                                                             X.sub.103 (R.sub.43 = C.sub.2 H.sub.4,                                        R.sub.45 = NH(CH.sub.2).sub.2-3N(C.sub.2 H.sub.5).sub.2)                      g                                                            228  T.sub.5                                                                             A.sub.2                                                                             X.sub.107                                                    229  H     A.sub.2                                                                             CONH(CH.sub.2).sub.2 CONH(CH.sub.2).sub.2 NHCO               230  T.sub.2                                                                             A.sub.2                                                                             CONH(CH.sub.2).sub.2 CONH(CH.sub.2).sub.2 NHCO               231  T.sub.3                                                                             A.sub.2                                                                             CONHC.sub.2 H.sub.4 NHCOCHCHCONHC.sub.2 H.sub.4 NHCO         232  T.sub.4                                                                             A.sub.3                                                                             CONHC.sub.2 H.sub.4 NHCOC.sub.2 H.sub.4 CONHC.sub.2                           H.sub.4 NHCO                                                 233  T.sub.5                                                                             A.sub.4                                                                             X.sub.107                                                    234  T.sub.5                                                                             A.sub.2                                                            235  T.sub.4                                                                             A.sub.2                                                                              ##STR181##                                                  236  T.sub.4                                                                             H     X.sub.11                                                     237  T.sub.4                                                                             H     X.sub.85                                                     238  T.sub.4                                                                             H     X.sub.82                                                     239  T.sub.4                                                                             H     X.sub.71                                                     240  T.sub.4                                                                             A.sub.2                                                                             X.sub.11                                                     241  T.sub.4                                                                             A.sub.2                                                                             X.sub.85                                                     242  T.sub.4                                                                             A.sub.2                                                                             X.sub.82                                                     243  T.sub.4                                                                             A.sub.2                                                                             X.sub.71                                                     ______________________________________                                    

Compounds of Examples 187 and 212 dye paper a red tone; Compounds ofExamples 188 to 190, 194 to 197, 199 to 201, 203 to 211, 214 to 216 to235, 237, 238, 240 to 243 dye paper a yellow tone; the compound ofExample 191 dyes paper a blue tone and compounds of Examples 192, 193,198, 202, 213, 217 to 218 and 236 to 239 dye paper an orange tone.

EXAMPLE 244

Using suitable starting compounds and a method analogous to that ofExample 107, a compound of the formula ##STR182## may be prepared. Thiscompound dyes paper a red-yellow tone.

EXAMPLES 245 TO 258

Compounds of formula ##STR183## in which the symbols are given in Table10 below and symbols A₂₋₄ and T₂₋₇ are given under Examples 13 to 44,B₂₋₁₁ are defined under Examples 47 to 64; K₁₋₁₇ are defined underExamples 163 to 186 and the symbols X₁₋₁₀₈ used in Table 10 are definedunder Examples 187 to 243.

Compounds of Examples 245, 252 and 258 dye paper a red tone, compoundsof Examples 246, 248, and 257 dye paper an orange tone, the compound ofExample 247 dyes paper a blue tone and the compounds of Examples 249 to251 and 253 to 256 dye paper a yellow tone.

                  TABLE 10                                                        ______________________________________                                        EX.                                                                           No.       T     R.sub.2   T.sub.1                                                                           B        X                                      ______________________________________                                        245       H     A.sub.2   T.sub.4                                                                           H        X.sub.1                                246       T.sub.2                                                                             A.sub.2   T.sub.5                                                                           B.sub.2  X.sub.2                                247       T.sub.3                                                                             A.sub.3   T.sub.6                                                                           B.sub.3  X.sub.10                               248       T.sub.4                                                                             H         H   B.sub.4  X.sub.11                               249       T.sub.5                                                                             A.sub.2   T.sub.4                                                                           B.sub.6  X.sub.51                               250       T.sub.6                                                                             A.sub.2   T.sub.5                                                                           B.sub.7  X.sub.53                               251       T.sub.7                                                                             A.sub.2   H   B.sub.9  X.sub.59                               252       T.sub.4                                                                             A.sub.4   T.sub.5                                                                           H        X.sub.70                               253       T.sub.5                                                                             A.sub.2   H   H        X.sub.81                               254       T.sub.4                                                                             A.sub.4   T.sub.2                                                                           B.sub.4  X.sub.82                               255       T.sub.5                                                                             A.sub.2   T.sub.4                                                                           H        X.sub.25                               256       T.sub.4                                                                             A.sub.4   T.sub.4                                                                           H        X.sub.86                               257       T.sub.4                                                                             A.sub.2   T.sub.4                                                                           .sub. B.sub.10                                                                         X.sub.11                               258       T.sub.4                                                                             A.sub.2   T.sub.4                                                                           .sub. B.sub.11                                                                         X.sub.70                               ______________________________________                                    

EXAMPLES 259 TO 268

Compounds of the formula ##STR184## in which the symbols are given inTable 11 below, may be prepared in a manner analogous to that of Example107

                  TABLE 11                                                        ______________________________________                                        EX.                                                                           No.        T     R.sub.2     X    K                                           ______________________________________                                        259        T.sub.4                                                                             A.sub.2     X.sub.1                                                                            K.sub.1                                     260        T.sub.5                                                                             A.sub.2     X.sub.6                                                                            K.sub.4                                     261        H     A.sub.4     X.sub.11                                                                           K.sub.5                                     262        T.sub.4                                                                             H           X.sub.18                                                                           K.sub.7                                     263        T.sub.5                                                                             A.sub.4     X.sub.55                                                                           K.sub.8                                     264        T.sub.4                                                                             A.sub.2     X.sub.59                                                                           K.sub.10                                    265        T.sub.6                                                                             A.sub.4     X.sub.70                                                                           K.sub.11                                    266        T.sub.7                                                                             A.sub.2     X.sub.82                                                                           K.sub.16                                    267        T.sub.4                                                                             A.sub.2     X.sub.85                                                                           K.sub.17                                    268        T.sub.5                                                                             A.sub.2     X.sub.11                                                                           K.sub.14                                    ______________________________________                                    

The compound of Example 262 dyes paper a red tone, compounds of Examples259 to 261 dye paper an orange tone and compounds of Examples 262 to 268dye paper a yellow tone.

EXAMPLE 269

Starting with a monoazo compound of formula (269a) ##STR185## andreacting with a cyanuric chloride derivative a compound of formula(269b) ##STR186## may be formed.

By reacting the compound of formula (269b) with the compound of formula(269c) ##STR187## in water at 90° C. and at pH 9, a compound of formula269d ##STR188## may be formed by a method analogous to that ofExample 1. The compound of Example 269d dyes paper a yellow tone.

EXAMPLE 270

A compound of formula 270a ##STR189## is diazotised and then coupled to2-amino-1,4-dimethylbenzene. The resulting disazo compound is furtherdiazotised and then coupled to a compound of the formula H--K₅##STR190## to form a compound formula 270b ##STR191##

This dyestuff dyes paper a brown tone. Instead of coupling to2-amino-1,4-dimethylbenzene, an equivalent amount of2-methoxy-5-methylaniline will produce a compound of formula 270c##STR192## results.

The compound 270c dyes paper a brown tone.

The compound 270c can be metallised by known methods with such metals ascopper, to form a compound of formula 270d ##STR193## where M_(e) iscopper.

EXAMPLES 271 TO 283

Compounds of the formula ##STR194## where the symbols are defined inTable 12 below may be made by a method analogous to that of Example 270and then metallised. Symbols B₂₋₁₁ are given under Examples 47 to 64 andsymbols A₂₋₄ and T₂₋₇ are given under Examples 13 to 44.

The compounds of Examples 271 to 273 and 277 to 281 dye paper a violettone and compounds of Examples 274 to 276 and 282 to 283 dye paper ablue tone.

                  TABLE 12                                                        ______________________________________                                        EX.                                                                           No.  T     R.sub.2                                                                              T.sub.1                                                                           B   X                                                   ______________________________________                                        271  T.sub.5                                                                             A.sub.2                                                                              T.sub.5                                                                           B.sub.8                                                                            ##STR195##                                         272  T.sub.4                                                                             A.sub.4                                                                              T.sub.3                                                                           B.sub.4                                                                            ##STR196##                                         273  T.sub.2                                                                             A.sub.2                                                                              T.sub.6                                                                           B.sub.6                                                                            ##STR197##                                         274  H     A.sub.2                                                                              T.sub.4                                                                           B.sub.8                                                                            ##STR198##                                         275  H     A.sub.2                                                                              T.sub. 5                                                                          H                                                                                  ##STR199##                                         276  T.sub.4                                                                             A.sub.2                                                                              T.sub.7                                                                           B.sub.2                                                                            ##STR200##                                         277  T.sub.4                                                                             H      T.sub.4                                                                           B.sub.6                                                                            ##STR201##                                         278  T.sub.5                                                                             A.sub.2                                                                              T.sub.4                                                                           B.sub.3                                                                            ##STR202##                                         279  T.sub.4                                                                             A.sub.2                                                                              T.sub.4                                                                           B.sub.8                                                                            ##STR203##                                         280  T.sub.4                                                                             A.sub.2                                                                              T.sub.4                                                                           B.sub.8                                                                            ##STR204##                                         281  T.sub.5                                                                             A.sub.4                                                                              T.sub.7                                                                           H                                                                                  ##STR205##                                         282  T.sub.4                                                                             A.sub.2                                                                              T.sub.4                                                                           B.sub.8                                                                            ##STR206##                                         283  T.sub.5                                                                             A.sub.4                                                                              T.sub.7                                                                           H                                                                                  ##STR207##                                         ______________________________________                                    

EXAMPLES 284 TO 297

In a similar manner to the method of Example 270, compounds of theformula ##STR208## where the symbols are defined in Table 13 below, canbe prepared. Symbols K₂₋₁₇ are defined under Examples 163 to 186.

The compounds of Examples 284 to 289 and 292 to 295 dye paper a violettone and compounds of Examples 290, 291, 296 and 297 dye paper a bluetone.

                  TABLE 13                                                        ______________________________________                                        EX.                                                                           No.  T      R.sub.2                                                                              K    X                                                     ______________________________________                                        284  T.sub.5                                                                              A.sub.2                                                                              K.sub.5                                                                             ##STR209##                                           285  T.sub.6                                                                              A.sub.4                                                                              K.sub.9                                                                             ##STR210##                                           286  H      H      K.sub.17                                                                            ##STR211##                                           287  T.sub.4                                                                              A.sub.2                                                                              K.sub.3                                                                             ##STR212##                                           288  T.sub.5                                                                              A.sub.2                                                                              K.sub.10                                                                            ##STR213##                                           289  T.sub.6                                                                              A.sub.2                                                                              K.sub.8                                                                             ##STR214##                                           290  T.sub.4                                                                              A.sub.2                                                                              K.sub.4                                                                             ##STR215##                                           291  T.sub.7                                                                              A.sub.4                                                                              K.sub.16                                                                            ##STR216##                                           292  T.sub.4                                                                              A.sub.2                                                                              K.sub.11                                                                            ##STR217##                                           293  T.sub.5                                                                              A.sub.4                                                                              K.sub.14                                                                            ##STR218##                                           294  T.sub.4                                                                              A.sub.2                                                                              K.sub.2                                                                             ##STR219##                                           295  T.sub.4                                                                              A.sub.2                                                                              K.sub.13                                                                            ##STR220##                                           296  T.sub.4                                                                              A.sub.2                                                                              K.sub.10                                                                            ##STR221##                                           297  T.sub.5                                                                              A.sub.2                                                                              K.sub.5                                                                             ##STR222##                                           ______________________________________                                    

EXAMPLES 298 TO 300

Compounds of the formula ##STR223## may be formed by diazotising acompound of formula 270a and then coupling with a compound H--K where Kis ##STR224##

The coupling components H--K can be made from known compounds by knownmethods.

EXAMPLE 301

(a) Preparation of a coupling component of formula 301a ##STR225##

91 Parts of cyanuric chloride are suspended in 240 parts of an ice/watermixture. 133 Parts of N,N-diethylamino propylamine is added dropwise at5° to 10° and the mixture is stirred for 3 hours after which 127 partsof 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid is added. Thetemperature is raised to 90° and the pH is held at 2.5 to 3 by theportionwise addition of 54 parts of sodium acetate. After 2 hourscondensation is terminated. The solution is allowed to cool whilststirring to 20° where the desired crystalline product deposits. Theproduct is filtered and 265 parts of a grey product results containing217 parts of the coupling component 301a.

(b) Preparation of an amino component of formula 301b ##STR226##

30 Parts of 4-aminoacetanilide are reacted in 500 parts of an ice/watermixture at 0° C. with 50 parts of concentrated hydrochloric acid. Afterthis addition, 55 parts of a 4N sodium nitrite solution is addeddropwise followed by 42 parts of 6-hydroxy-4-methyl-3-pyridiniumpyrid-2-one and this mixture is brought to pH 6 by the addition ofsodium carbonate. Coupling occurs immediately and an orange dyestuffresults. After coupling is completed the compound is filtered and theresulting press cake is suspended in 300 parts of water and then reactedwith 100 parts of concentrated hydrochloric acid and heated to 95° C.The splitting off of the acetyl group is completed after 2 hours. Theresulting solution is cooled to room temperature by stirring and thedyestuff of formula 301b falls out as yellow crystals. This is filtered,washed with brine and dried. 170 Parts of a yellow powder resultscontaining 68 parts of the compound of formula 301b.

(c) Preparation of a compound of formula 301c ##STR227##

20.5 Parts of the compound of formula 301a are suspended in 200 parts ofwater and dissolved therein by the addition of sodium hydroxide.

22.4 Parts of the compound of formula 301b is diazotised by knownmethods and the resulting diazo solution is added dropwise to thecompound of formula 301a, and the pH of the reaction is held at 8 to 9by the addition of sodium hydroxide. Coupling occurs immediately to givea blue dyestuff. After termination of coupling the pH is reduced to 7.5by the dropwise addition of concentrated hydrochloric acid and thedyestuff precipitates completely and then is filtered and dried. Thedyestuff is blue in colour and in the form of its acid addition saltdyes paper a blue colour. The remaining dyebath is colourless. Thewet-fastnesses of the dyeings so produced are good.

EXAMPLE 302

The compound of formula 301c may be prepared by coupling4-aminoacetanilide to the compound of formula 301a, followed bysaponifying in acid medium, diazotising and then coupling to6-hydroxy-4-methyl-3-pyridinium-pyrid-2-one.

EXAMPLE 303

Instead of using 4-aminoaniline in the method of Example 301,p-nitroaniline is used, followed by reducing the nitro group in analkali medium of a sulphuric acid salt. The resulting dyestuff is offormula 301c.

EXAMPLES 304 TO 340

Compounds of the formula ##STR228## in which the symbols are defined inTable 14 below, can be prepared by methods analogous to Examples 301 to303.

In these Examples ##STR229##

In group X the starred carbon atom is attached to the azo group attachedto the pyridone.

In column I the numbers 1 to 9 represent the colour of the compound ofthe particular Example.

    ______________________________________                                        1 = orange   2 = blueish-red                                                                            3 = reddish-blue                                    4 = blue     5 = grey-blue                                                                              6 = red-violet                                      7 = blue-violet                                                                            8 = violet   9 = brown                                           ______________________________________                                    

The position of groups is given by a figure in parentheses.

                                      TABLE 14                                    __________________________________________________________________________                                             n and                                                                         pos. of                              EX.                                      SO.sub.3 H                                                                        R.sub.1a and position of         No.                                                                              R                   X                 group                                                                             R.sub.1a group  I                __________________________________________________________________________    304                                                                               ##STR230##                                                                                        ##STR231##       1 (3)                                                                             NHC.sub.3 H.sub.6 N(CH.sub.3)                                                 .sub.2 (6)      8                305                                                                              "                   "                 "   NHY.sub.1 (6)   7                306                                                                              "                   "                 "   NHY.sub.2 (6)   7                307                                                                              "                   "                 "   NHY.sub.4 (6)   7                308                                                                              "                   "                 "   NHY.sub.1 (7)   5                309                                                                              "                   "                 "   NHY.sub.3 (7)   5                310                                                                              "                   "                 "                                                                                  ##STR232##     6                311                                                                              "                   "                 2 (3;6)                                                                           NHY.sub.2 (8)   4                312                                                                              "                   "                 "   NHY.sub.3 (8)   4                313                                                                              "                   "                 "   NHY.sub.4 (8)   4                314                                                                              "                                                                                                  ##STR233##       1 (3)                                                                             NHY.sub.1 (6)   1                315                                                                              "                   "                 "   NHY.sub.2 (6)   1                316                                                                              "                   "                 2 (3;6)                                                                           NHY.sub.1 (8)   6                317                                                                              "                   "                 "   NHY.sub.3 (8)   6                318                                                                              "                                                                                                  ##STR234##       "   NHY.sub.1 (8)   4                319                                                                              "                   "                 "   NHY.sub.2 (8)   4                320                                                                              "                                                                                                  ##STR235##       "   NHY.sub.1 (8)   4                321                                                                              "                                                                                                  ##STR236##       "   "               4                322                                                                              "                                                                                                  ##STR237##       "   "               4                323                                                                              "                                                                                                  ##STR238##       "   "               4                324                                                                              "                                                                                                  ##STR239##       "   "               4                325                                                                              "                   "                 "   NHY.sub.2 (8)   4                326                                                                              "                                                                                                  ##STR240##       "   NHY.sub.1 (8)   3                327                                                                               ##STR241##                                                                                        ##STR242##       "   "               4                328                                                                              "                   "                 "   NHY.sub.2 (8)   4                329                                                                               ##STR243##         "                 "   NHY.sub.1 (8)   4                330                                                                               ##STR244##         "                 "   "               3                331                                                                               ##STR245##         "                 "   "               4                332                                                                              "                   "                 "   NHY.sub.2 (8)   4                333                                                                               ##STR246##         "                 "   NHY.sub.1 (8)   4                334                                                                               ##STR247##         "                 "   "               4                335                                                                               ##STR248##         "                 "   "               4                336                                                                               ##STR249##                                                                                        ##STR250##       "   "               9                337                                                                              "                   "                 "   NHY.sub.3 (8)   9                338                                                                              "                                                                                                  ##STR251##       "   NHY.sub.1 (8)   4                339                                                                               ##STR252##                                                                                        ##STR253##       1 (4)                                                                             H               2                340                                                                               ##STR254##         "                 0   NHY.sub.1 (4)   2                __________________________________________________________________________

EXAMPLE 341

Starting with a compound of formula 341a ##STR255## a compound offormula 341b ##STR256## can be prepared as follows.

The compound of formula 341a can be made by an analogous method to thatof Example 45.

75 Parts of a compound of formula 341a are diazotised with 3 parts of a4N sodium nitrite solution to which an alkali solution containing 2.5parts of 5,5'-dihydroxy-7,7'-disulpho-2,2'-dinaphthyl urea is addeddropwise. Coupling is fully completed by the addition of 10 parts ofNaOH and a compound of formula 341b results having a blue tone.

EXAMPLES 342 TO 348

Compounds of the formula ##STR257## can be prepared by a methodanalogous to that of Example 341 using suitable starting materials. Thesymbols are defined in Table 15 below. In column I the colour numeralsin column I are as for Examples 304 to 340 with additionally10=brownish-red and 11=black.

                                      TABLE 15                                    __________________________________________________________________________    EX.                                                                           No.                                                                              T        B          K                           I                          __________________________________________________________________________    342                                                                               ##STR258##                                                                            (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                 ##STR259##                 10                         343                                                                              "        (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                       "                           10                         344                                                                              "        "                                                                                         ##STR260##                  8                         345                                                                              "        "                                                                                         ##STR261##                  4                         346                                                                               ##STR262##                                                                            (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                        ##STR263##                 11                         347                                                                              CN                                                                                      ##STR264##                                                                              "                           11                         348                                                                              "                                                                                       ##STR265##                                                                              "                           11                         __________________________________________________________________________

EXAMPLE 349

From appropriate starting compounds, a compound of formula 349a##STR266## can be prepared. The compound 349a dyes paper a grey-violettone.

EXAMPLE 350

10 Parts of the dyestuff of Example 318 are stirred in 200 parts ofwater and warmed to 80°. A solution of 3 parts copper sulphatepentahydrate in 20 parts water and 15 parts of concentrated ammonia ispoured into the dyestuff solution and the temperature is raised to 90°to 95°. After 4 hours metallisation is terminated, 30 parts of NaCl areadded, the mixture is cooled to room temperature and finally 5 parts ofsodium hydroxide are added dropwise.

A dyestuff of formula 350a ##STR267## results. In acid addition saltform compound 350a dyes paper a grey brown tone. The spent liquor ispractically colourless and the wet fastnesses and light fastnesses areexcellent.

EXAMPLE 351

28 Parts of compound 301c powder are dissolved in 90 parts of water and10 parts of lactic acid whilst stirring at 60°. Then the dyestuffsolution is clear-filtered. One obtains 125 parts of a filtrate which isstable to storage for several months and which neither under warm norcold conditions allows the dyestuff to be deposited. This dyestuffsolution may be used directly (or thinned with water) in dyeing paper.

EXAMPLE 352

24 Parts of the compound 301c powder are stirred into 500 parts of waterand then the mixture is acidified with 5 parts of glacial acetic acid.The dyestuff dissolves in solution and then the solution is dried. Acompound of formula 352a R2 ? ? ? ##STR268## results, having in powderform a high solubility in cold water.

In Examples 351 and 352 instead of the acids used, such acids ashydrochloric, sulphuric, phosphoric and formic acids may be used andinstead of the dyestuff 301c any of the compounds of Examples 302 to 350may be used.

EXAMPLE 353

80 Parts of the dyestuff of 301c powder are stirred into a solution of20 parts dextrin, 20 parts of glacial acetic acid and 300 parts of waterand a homogeneous suspension suspension results. The mixture is atomisedand a blue granulate results having good handle properties and littledust. Paper can be dyed a blue tone by adding the granulate to a papermass.

In a similar fashion a granulate may be made from any one of compoundsof Examples 1 to 299 and 302 to 350.

EXAMPLE 354

In 600 parts of water 22.2 parts (0.05 mols) of a compound of theformula 354a ##STR269## in hydrochloric acid medium are diazotised with3.45 parts (0.05 mols) of sodium nitrite at 0°-5°. To this solution 15.9parts (0.05 mols) of 1 amino-8-hydroxynaphthalene-3,6 disulphonic acidare added dropwise, dissolved in 150 parts of water and 3 parts ofsodium carbonate. The solution has a pH of 1.5. By the addition of 10parts of sodium acetate over 12 hours the pH is brought to 2.3. Theresulting dyestuff is of formula 354b ##STR270##

22 Parts (0.05 mols) of 2,4bis-(diethylaminopropylamino)-6-(3'-aminophenylamino)-s-triazine inhydrochloric acid medium are diazotised in aqueous medium with 3.45parts (0.05 mols) of sodium nitrite at 0°-5° and are then added to thecompound of formula 354b in acid medium.

By the addition of 45 parts of a 30% aqueous NaOH solution the pH isbrought to 8.5-9. After coupling has finished a dyestuff of the formula354c ##STR271## is obtained. This compound 354c dyes paper and leather ablack tone.

EXAMPLE 355

22 Parts (0.05 mols) of2,4-bis(diethylaminopropylamino)-6-(3'-aminophenylamino)-3-triazine inhydrochloric acid medium are diazotised in aqueous medium with 3.45parts (0.05 mols) of sodium nitrite at 0°-5°. This is then added in acidmedium to 1-amino-8-hydroxynaphthalene 3,6-disulphonic acid and then22.2 parts of the compound of formula 354a (from Example 354) are addedin alkali medium to produce the compound of formula 355a ##STR272##

This is an isomeric form of the compound 354c and also dyes paper andleather a black tone.

Both dyes 354c and 355a have good fastness properties.

EXAMPLES 356-380

Compounds of the formula ##STR273## in which the symbols are defined inTable 16 can be formed by a method analogous to that of Example 354 orExample 355 from appropriate starting materials. In these Examples thesymbols A₃₃₋₄₂ are as defined below. ##STR274##

                                      TABLE 1b                                    __________________________________________________________________________             Positions                                                                          Position                                                                 and sig-                                                                           of --N═N    Position and                                    Ex.      nificance                                                                          on ring         significance                                    No. T B  of R.sub.62                                                                        G     R.sub.60a                                                                        R.sub.60b                                                                        R.sub.63                                                                          of R.sub.64                                     __________________________________________________________________________    356 T.sub.4                                                                         A.sub.33                                                                         H    4     OH NH.sub.2                                                                         H   4-A.sub.38                                      357 T.sub.4                                                                         "  H    4     NH.sub.2                                                                         OH H   4-A.sub.38                                      358 T.sub.4                                                                         "  H    3     OH NH.sub.2                                                                         H   3-A.sub.38                                      359 T.sub.4                                                                         "  H    3     NH.sub.2                                                                         OH H   3-A.sub.38                                      360 T.sub.4                                                                         "  H    3     OH NH.sub.2                                                                         H   4-A.sub.38                                      361 T.sub.4                                                                         "  H    3     NH.sub.2                                                                         OH H   4-A.sub.38                                      362 T.sub.2                                                                         A.sub.35                                                                         H    4     OH NH.sub.2                                                                         H   3-A.sub.38                                      363 T.sub.5                                                                         "  H    4     OH NH.sub.2                                                                         H   3-A.sub.38                                      364 T.sub.4                                                                         A.sub.34                                                                         H    4     OH NH.sub.2                                                                         H   3-A.sub.38                                      365 T.sub.4                                                                         A.sub.35                                                                         H    4     OH NH.sub.2                                                                         H   3-A.sub. 38                                     366 T.sub.4                                                                         A.sub.36                                                                         H    4     OH NH.sub.2                                                                         H   3-A.sub.38                                      367 T.sub.4                                                                         A.sub.37                                                                         H    4     OH NH.sub.2                                                                         H   3-A.sub.38                                      368 T.sub.4                                                                         A.sub.35                                                                         H    4     OH NH.sub.2                                                                         H   3-A.sub.39                                      369 T.sub.4                                                                         "  H    4     OH NH.sub.2                                                                         H   3-A.sub.40                                      370 T.sub.4                                                                         "  H    4     OH NH.sub.2                                                                         H   3-A.sub.41                                      371 T.sub.4                                                                         "  H    4     OH NH.sub.2                                                                         H   3-A.sub.42                                      372 T.sub.4                                                                         A.sub.33                                                                         OH(4)                                                                              3     OH NH.sub.2                                                                         H   3-A.sub.38                                      373 T.sub.4                                                                         "  OH(4)                                                                              3     OH NH.sub.2                                                                         H   3-A.sub.38                                      374 T.sub.4                                                                         "  OH(3)                                                                              4     OH NH.sub.2                                                                         H   3-A.sub.38                                      375 T.sub.4                                                                         "  OH(3)                                                                              4     OH NH.sub.2                                                                         H   3-A.sub.38                                      376 T.sub.4                                                                         A.sub.35                                                                         H    4     NH.sub.2                                                                         OH OH  3-A.sub.42                                      377 T.sub.4                                                                         "  H    4     NH.sub.2                                                                         OH OH  3-A.sub.42                                      378 T.sub.4                                                                         "  H    4     NH.sub.2                                                                         OH OCH.sub.3                                                                         3-A.sub.42                                      __________________________________________________________________________

APPLICATION EXAMPLE A

70 Parts of chemically bleached sulphite cellulose obtained frompinewood and 30 parts of chemically bleached sulphite cellulose obtainedfrom birchwood are ground in 2000 parts of water in a Hollander. 0.5Parts of the dyestuff from Example 301 of formula 301c (as an acidaddition salt, e.g. Example 351) are sprinkled into this pulp. Paper isproduced from this pulp after mixing for 20 minutes. The absorbent paperwhich is obtained in this manner is dyed in a blue tone. The waste wateris practically colourless.

APPLICATION EXAMPLE B

0.5 Parts of the dyestuff from Example 301 of formula 301c (as an acidaddition salt, e.g. Example 351) are added to 100 parts of chemicallybleached sulphite cellulose which have been ground in a Hollander with200 parts of water. Sizing takes place after thorough mixing for 15minutes. The paper which is produced from this material has a blue toneand good light- and wet-fastnesses.

APPLICATION EXAMPLE C

An absorbent length of unsized paper is drawn at 40 to 50° C. through adyestuff solution having the following composition:

0.5 parts of the dyestuff from Example 314 (as an acid addition salt)

0.5 parts of starch and

99.0 parts of water.

The excess dyestuff solution is squeezed out through two rollers. Thedried length of paper is dyed in an orange tone.

APPLICATION EXAMPLE D

100 Parts freshly tanned and neutralised chrome leather are agitated for30 minutes in a vessel with a dyebath of 250 parts water at 55° C. and0.5 parts of the dyestuff of Examples 346 in acid addition salt form,and then treated in the same bath for 30 minutes with 2 parts of ananionic fatty liquor based on sulphonated train oil. The leather is thendried and prepared in the normal way, giving a leather evenly dyed in ablack tone.

Other low affinity vegetable-tanned leathers can similarly be dyed byknown methods.

APPLICATION EXAMPLE E

2 Parts of the dyestuff of Example 350 in acid addition salt form aredissolved in 4000 parts demineralised water at 40° C. 100 Parts of apre-wetted cotton textile substrate are added, and the bath is raised toboiling point over 30 minutes and held at the boil for 1 hour. Afterrinsing and drying, a greyish-blue dyeing is obtained having good light-and wet-fastnesses. The dye exhausts practically totally, and the wastewater is almost colourless.

The dyestuffs of any of the other Examples may be used in place of thecompound of the particular Example named in any one of ApplicationExamples A to C (if Examples 301 to 353 then in acid addition saltform). The dyes so used may be in the form of solid or liquidpreparations.

What is claimed is:
 1. A metal-free compound of the formula ##STR275##or a 1:1 or 1:2 metal complex thereof, or an acid addition salt of ametal-free compound of said formula or a 1:1 or 1:2 metal complexthereof,wherein B is hydrogen; C₁₋₄ alkyl; C₁₋₄ alkyl monosubstituted byC₁₋₄ alkoxy; C₂₋₄ alkyl substituted by hydroxy; C₅₋₆ cycloalkyl; C₅₋₆cycloalkyl substituted by 1 to 3 C₁₋₄ alkyl groups; phenyl(C₁₋₃ alkyl);phenyl(C₁₋₃ alkyl) the phenyl group of which is substituted by 1 to 3substituents selected from C₁₋₄ alkyl, C₁₋₄ alkoxy and halo; --A--NH--R₂; --A₄ '--N(R₇)₂ ; --A₄ --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ or --N(R₇)₂, whereinAis linear or branched C₂₋₈ alkylene; linear or branched C₂₋₈ alkyleneinterrupted by 1 or 2 hetero atoms; linear or branched C₂₋₈ alkenylene;linear or branched C₂₋₈ alkenylene interrupted by 1 or 2 hetero atoms;phenylene or cyclohexylene, A₄ is linear or branched C₂₋₈ alkylene orlinear or branched C₂₋₈ alkenylene, A₄ ' is linear or branched C₁₋₈alkylene or linear or branched C₂₋₈ alkenylene, and R₂ is ##STR276##wherein R₁₁ is hydrogen, halo, nitro, C₁₋₄ alkyl or C₁₋₄ alkoxy, andR₁₂is --CO--(CH₂)_(a) --Z or ##STR277## wherein Z is --N(R₇)₂ or --N.sup.⊕(R₈)₂ R₉ A.sup.⊖, and a is 1, 2 or 3, R is hydrogen; C₁₋₄ alkyl; C₅₋₆cycloalkyl; C₅₋₆ cycloalkyl substituted by 1 or 2 C₁₋₄ alkyl groups;phenyl; phenyl substituted by 1 or 2 substituents selected from methyl,ethyl, methoxy and ethoxy; benzyl; phenylethyl; or benzyl or phenylethylthe phenyl group of which is substituted by 1 or 2 substituents selectedfrom methyl, ethyl, methoxy and ethoxy, R₁ is hydrogen or --N═N--D,wherein D is a diazo component radical, with the proviso that R₁ must be##STR278## when B is other than --A--NH--R₂, whereinA₁ is a tetrazocomponent radical, R₁₇ is hydrogen, --N═N--K₁, --N═N--A₁₀ --N═N--K₁,##STR279## wherein A₁₀ is a tetrazo component radical or acoupling/diazo component radical,K₁ is a diazo component radical or acoupling component radical, R₂₀ is --(NR₅)_(q) --Q₁ --N(R₇)₂,--(NR₅)_(q) --Q₂ --N.sup.⊕ (R₈)₂ R₉ A.sup.⊖ or ##STR280## wherein Q₁ islinear or branched C₂₋₆ alkylene, --CH₂ C*O-- or --CH₂ --CON*H--,wherein the * denotes the atom attached to the --(NR₅)_(q) -- radical,andQ₂ is linear or branched C₂₋₆ alkylene, --CH₂ C*O--, --CH₂ CON*H-- or--CH₂ CONHC*O--, wherein the * denotes the atom attached to the--(NR₅)_(q) -- radical, X_(o) is a bridging radical, R₁₉ is hydrogen;hydroxy; amino; (C₁₋₄ alkyl)carbonylamino; benzoylamino; phenylamino; orbenzoylamino or phenylamino the phenyl group of which is substituted by1 or 2 substituents selected from halo, nitro, amino, C₁₋₄ alkyl andC₁₋₄ alkoxy, with the proviso that R₁₉ must be hydrogen when R₁₇ isother than --N═N--K₁ and --N═N--A₁₀ --N═N--K₁, and R₆₀ is hydroxy oramino, and R_(60a) is hydrogen, hydroxy or amino, with the proviso thatR_(60a) is hydrogen or amino when R₆₀ is hydroxy and is hydroxy when R₆₀is amino, and T is hydrogen, cyano, --COOR₄, --CO--N(R₅)₂, --SO₂--N(R₅)₂, ##STR281## wherein each R₃ is independently hydrogen, C₁₋₄alkyl, --N(R₅)₂ or --CO--N(R₅)₂,R₄ is C₁₋₆ alkyl or phenyl(C₁₋₃ alkyl),R₆ is C₁₋₄ alkyl, and X_(a) is --O--, --NR₅ -- or --S--,wherein each R₅is independently hydrogen or C₁₋₄ alkyl or, when two R₅ 's are attachedto a nitrogen atom, both R₅ 's taken together and with the nitrogen atommay form a saturated ring containing 1 to 3 hetero atoms, each R₇ isindependently hydrogen; C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo,hydroxy or cyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenylgroup of which is substituted by 1 to 3 substituents selected from halo,C₁₋₄ alkyl and C₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkylsubstituted by 1 or 3 C₁₋₄ alkyl groups, or both R₇ 's taken togetherand with the nitrogen atom to which they are attached form a 5- or6-membered saturated ring containing 1 to 3 hetero atoms, each R₈ isindependently C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo, hydroxy orcyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenyl group of whichis substituted by 1 to 3 substituents selected from halo, C₁₋₄ alkyl andC₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkyl substituted by 1 or 3C₁₋₄ alkyl groups, each R₉ is independently C₁₋₄ alkyl or C₁₋₄ alkylsubstituted by phenyl or both R₈ 's and R₉ taken together and with thenitrogen atom to which they are attached are pyridinium; pyridiniumsubstituted by 1 or 2 C₁₋₄ alkyl groups; or a 5- or 6-membered saturatedring containing 1 to 3 hetero atoms, each R₁₃ is independently amino; analiphatic, cycloaliphatic, aromatic or heterocyclic amino group thenitrogen atom of which is attached to the 1,3,5-triazine ring; halo;hydroxy; C₁₋₄ alkoxy; phenyl or ##STR282## wherein A₂ is linear orbranched C₂₋₆ alkylene or --N*HCOCH₂ --,wherein the * denotes the atomattached to the --NR₅ -- radical, and R, R₁, R₅ and T are as definedabove, each R₁₄ is independently an aliphatic, cycloaliphatic, aromaticor heterocyclic amino group the nitrogen atom of which is attached tothe 1,3,5-triazine ring, each n is independently 0, 1 or 2, each q isindependently 0 or 1, and each A.sup.⊖ is independently anon-chromophoric anion,with the provisos that (i) when the compound ofFormula I is a monoazo compound free of sulfo groups, it contains atleast one water-solubilizing basic or cationic group, (ii) when thecompound of Formula I is free of sulfo groups and is other than amonoazo compound, it contains at least two water-solubilizing groups,and (iii) when the compound of Formula I contains one or more sulfogroups, the total number of basic and cationic groups exceeds the numberof sulfo groups by at least one.
 2. A compound according to claim 1having the formula ##STR283## wherein A.sup.⊖ is a non-chromophoricanion.
 3. A metal-free compound, 1:1 or 1:2 metal complex or acidaddition salt according to claim 1 wherein T is hydrogen, cyano,--CO--N(R₅ ')₂ or ##STR284## wherein each R₃ ' is independentlyhydrogen, methyl, ethyl, amino or dimethylamino, andeach R₅ ' isindependently hydrogen, methyl or ethyl.
 4. A metal-free compound, 1:1or 1:2 metal complex or acid addition salt according to claim 1wherein Bis hydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl,--(CH₂)_(a) --N(R₇ ')₂, --(CH₂)_(b) --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖ or--A'--NH--R₂ ', whereinA' is linear or branched C₂₋₈ alkylene orphenylene, R₂ ' is ##STR285## wherein R₁₁ ' is hydrogen, chloro, nitro,methyl or methoxy,R₁₂ ' is --CO--(CH₂)_(t) --Z' or ##STR286## whereinR₁₃ ' is chloro, hydroxy, amino, N,N-di-(C₂₋₄ hydroxyalkyl)amino, --NR₅'R₂₁, ##STR287## wherein R₁₁ ' is as defined above, R₁₄ ' is --NR₅ 'R₂₁,##STR288## Z' is --N(R₇ ')₂ or --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, wherein R₇', R₈ ' and R₉ ' are as defined below, andt is 1 or 2, and q is 0 or 1,each R₇ ' is independently hydrogen, C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl),benzyl or 2-cyanoethyl or --N(R₇ ')₂ is pyrrolidino, piperidino,morpholino, piperazino or N'-methylpiperazino, each R₈ ' isindependently C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl,and R₉ ' is methyl, ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ ' ispyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR289##wherein Z_(o) is a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂--, --NH--, --NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, andR₉ ' is as definedabove, a is 1, 2 or 3, and b is 2 or 3,wherein R₅ ' is hydrogen, methylor ethyl, and R₂₁ is C₁₋₁₂ alkyl; C₂₋₁₂ alkyl substituted by hydroxy;C₃₋₁₂ alkyl interrupted by 1 to 3 radicals selected from --NR₇ -- and--N.sup.⊕ (R₈)₂ --A.sup.⊖ ; --NHCO--CH₂ --Z; --CH₂ --CONH--Y₁ --Z; --Y₁--Z; ##STR290## wherein R₂₃ is halo, hydroxy, nitro, C₁₋₄ alkyl or C₁₋₄alkoxy,R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, --CO--Y₂ --Z',--NHCO--Y₂ --Z', --CONH--Y₂ --Z'--SO₂ NH--Y₂ --Z', --Y₂ --Z' or--NHNHCO--CH₂ --Z', whereinY₂ is linear or branched C₁₋₈ alkylene, andR₇ ', R₈ ', R₉ ' and Z' are as defined above, each Y₁ is independentlylinear or branched C₁₋₈ alkylene or linear or branched C₃₋₈ alkenylene,Z' is as defined above, and R₇, R₈ and Z are as defined in claim1,wherein each R_(5a) is independently hydrogen or C₁₋₄ alkyl, each R₆is independently C₁₋₄ alkyl, and each A.sup.⊖ is independently anon-chromophoric anion.
 5. A metal-free compound, 1:1 or 1:2 metalcomplex or acid addition salt according to claim 1 wherein R is methyl,ethyl, phenyl, benzyl or cyclohexyl.
 6. A metal-free compound accordingto claim 1 having the formula ##STR291## or a 1:1 or 1:2 metal complexthereof, or an acid addition salt of a metal-free compound of saidformulaor a 1:1 or 1:2 metal complex thereof, wherein A₁ ' is ##STR292##wherein R₅₁ is hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,R₅₂ ishydrogen, hydroxy, halo, cyano, --CONH₂, (C₁₋₄ alkyl)carbonylamino,--NHCONH₂, carboxy, sulfo, C₁₋₄ alkyl or C₁₋₄ alkoxy, each R₅₃ isindependently hydrogen, halo, cyano, C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy,sulfo or hydroxy, and Y_(o) is a direct bond, --(CH₂)_(a) --, --O--,--S--, --SO₂ --, --NHCO--, --NHCONH--, --NHCO--(CH₂)_(b) --CONH--,--CONH--(CH₂)_(b) --NHCO--, --O--(CH₂)_(b) --O--, --N═N-- or--CH═CH--CO--CH═CH--, B₁ ' is hydrogen, methyl, ethyl, hydroxyethyl,cyclohexyl, benzyl, --(CH₂)_(b) --N(R₇ ")₂ or --(CH₂)_(b) --N.sup.⊕ (R₈")₂ R₉ "A.sup.⊖, whereineach R₇ " is independently hydrogen, methyl,ethyl or 2-hydroxyethyl or --N(R₇ ")₂ is morpholino, piperidino,piperazino or N'-methylpiperazino, each R₈ " is independently methyl,ethyl or 2-hydroxyethyl, and R₉ " is methyl, ethyl or benzyl or--N.sup.⊕ (R₈ ")₂ R₉ " is pyridinium, pyridinium substituted by 1 or 2methyl groups or ##STR293## wherein R₉ ' and Z_(o) are as defined below,R' is methyl, ethyl, phenyl, benzyl or cyclohexyl, R_(17a) is --N═N--K₁', --N═N--A₁ '--N═N--K₁ ' or ##STR294## wherein K₁ ' is ##STR295##wherein K_(b) is ##STR296## wherein each R₂₈ is independently hydrogen,halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,R₂₉ is --(CH₂)_(m) --Z, ##STR297##wherein R₄₆ is hydrogen, --NHCO--(CH₂)_(b) --Z, --SO₂ NH--(CH₂)_(b) --Z,--CO--Y₁ --Z or ##STR298## each R₄₇ is independently hydrogen, halo,C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro or cyano, andR₄₈ is C₁₋₄ alkoxy, R₃₂ isC₁₋₄ alkyl or phenyl, each R₃₃ is independently hydrogen, C₁₋₄ alkyl,--(CH₂)_(b) --OCH₃, 2-hydroxyethyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b)--N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ is amino or hydroxy, R₃₅ is C₁₋₄ alkyl,--COOR₆, --CO--N(R_(5a))₂ or --CONH--Y₁ --Z, R₃₆ is hydrogen, ##STR299##wherein R₄₉ is hydrogen, --CONH--Y₁ --Z, --SO₂ NH--Y₁ --Z,--NHCO--(CH₂)_(b) --Z or ##STR300## and each R₅₀ is independentlyhydrogen, halo, C₁₋₄ alkoxy, C₁₋₄ alkyl, nitro or amino, R₃₇ ishydrogen, --NHCO--(CH₂)_(a) --Z, --SO₂ NH--Y₁ --Z, --CONH--Y₁ --Z,--CONHNH₂, --NH--Y₁ --Z, --CH₂ --Z, --NHNHCO--CH₂ --Z,nitrophenylcarbamoyl or ##STR301## R₃₈ is C₁₋₄ alkyl, benzyl or2-cyanoethyl, R₃₉ is C₁₋₄ alkyl or --(CH₂)_(m) --Z, each R₄₀ isindependently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₆₃ is hydrogen,chloro, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or hydroxy, R₆₄ is hydrogen,dimethylamino, trimethylammonium A.sup.⊖, diethylamino, triethylammoniumA.sup.⊖, --CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂ --Z, --NHCO--Y₂ --Z, --SO₂NH--Y₂ --Z, --NHNHCO--CH₂ --Z or ##STR302## R' is as defined above, andB' and T' are as defined below, X_(o) ' is --NH--, --NHCONH--,--NHCO--CH═CH--CONH--, --NHCO--(CH₂)_(b) --CONH--, ##STR303## , and A₁ 'is as defined above, and T' is hydrogen, cyano, --CO--N(R₅ ')₂ or##STR304## wherein each R₃ ' is independently hydrogen, methyl, ethyl,amino or dimethylamino, andeach R₅ ' is independently hydrogen, methylor ethyl,wherein B' is hydrogen, methyl, ethyl, hydroxyethyl,cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂, --(CH₂)_(b) --N.sup.⊕ (R₈')₂ R₉ 'A.sup.⊖ or --A'--NH--R₂ ', whereinA' is linear or branched C₂₋₈alkylene or phenylene, R₂ ' is ##STR305## wherein R₁₁ ' is hydrogen,chloro, nitro, methyl or methoxy,R₁₂ ' is --CO--(CH₂)_(t) --Z' or##STR306## wherein is chloro, hydroxy, amino, N,N-di-(C₂₋₄-hydroxyalkyl)amino, --NR₅ 'R₂₁, ##STR307## wherein R₁₁ ' is as definedabove, R₁₄ ' is --NR₅ 'R₂₁, ##STR308## Z' is --N(R₇ ')₂ or --N.sup.⊕ (R₈')₂ R₉ 'A.sup.⊖, wherein R₇ ', R₈ ' and R₉ ' are as defined below, andtis 1 or 2, each R₇ ' is independently hydrogen, C₁₋₆ alkyl,n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl or --N(R₇ ')₂ ispyrrolidino, piperidino, morpholino, piperazino or N'-methylpiperazino,each R₈ ' is independently C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or2-cyanoethyl, and R₉ ' is methyl, ethyl, propyl or benzyl or --N.sup.⊕(R₈ ')₂ R₉ ' is pyridinium, pyridinium substituted by 1 or 2 methylgroups or ##STR309## wherein Zo is a direct bond, --CH₂ --, --O--,--S--, --SO--, --SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖,andR₉ ' is as defined above, whereinR₅ ' is hydrogen, methyl or ethyl,and R₂₁ is C₁₋₁₂ alkyl; C₂₋₁₂ alkyl substituted by hydroxy; C₃₋₁₂ alkylinterrupted by 1 to 3 radicals selected from --NR₇ -- and --N.sup.⊕(R₈)₂ --A.sup.⊖ ; --NHCO--CH₂ --Z; --CH₂ --CONH--Y₁ --Z; --Y₁ --Z;##STR310## wherein R₂₃ is halo, hydroxy, nitro, C₁₋₄ alkyl or C₁₋₄alkoxy,R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, --CO--Y₂ --Z',--NHCO--Y₂ --Z', --CONH--Y₂ --Z' --SO₂ NH--Y₂ --Z', --Y₂ --Z' or--NHNHCO--CH₂ --Z',wherein R₇ ', R₈ ' and R₉ ' are as defined above,wherein each R_(5a) is independently hydrogen or C₁₋₄ alkyl, each R₆ isindependently C₁₋₄ alkyl, each R₇, R₈, R₁₃, R₁₄ and Z is independentlyas defined in claim 1, each R₁₃ ', R₁₄ ' and Z' is independently asdefined above, each Y₁ is independently linear or branched C₁₋₈ alkyleneor linear or branched C₃₋₈ alkenylene, each Y₂ is independently linearor branched C₁₋₈ alkylene, each a is independently 1, 2 or 3, each b isindependently 2 or 3, each m is independently 1, 2, 3, 4, 5 or 6, each qis independently 0 or 1, and each A.sup.⊖ is independently anon-chromophoric anion.
 7. A metal-free compound according to claim 1having the formula ##STR311## or a 1:1 or 1:2 metal complex thereof, oran acid addition salt of a metal-free compound of said formula or a 1:1or 1:2 metal complex thereof,wherein A" is 1,2-ethylene, 1,3-propylene,1,3-phenylene or 1,4-phenylene, R" is methyl or phenyl, R₁ "' ishydrogen or --N═N--D", whereinD" is ##STR312## wherein K_(a) " is##STR313## R₁₇ ' is hydrogen, ##STR314## --N═N--K₁ ', --N═N--A₁'--N═N--K₁ ' or ##STR315## wherein R₂₀ ' is --NR₅ '--Q₁ --N(R₇ ')₂,--NR₅ '--Q₂ --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖ or ##STR316## R₂ " is##STR317## wherein R₁₂ " is --CO--CH₂ --Z" or ##STR318## wherein R₁₃ "is --NR₅ "R₂₁ ", ##STR319## R₁₄ " is --NR₅ "R₂₁ ', ##STR320## and Z" is--N(R₇ ")₂ or --N.sup.⊕ (R₈ ")₂ R₉ "A.sup.⊖, and R" is cyano or##STR321## wherein R₃ " is hydrogen or methyl,wherein each A₁ ' isindependently ##STR322## wherein R₅₁ is hydrogen, halo, C₁₋₄ alkyl orC₁₋₄ alkoxy,R₅₂ is hydrogen, hydroxy, halo, cyano, --CONH₂, (C₁₋₄alkyl)carbonylamino, --NHCONH₂, carboxy, sulfo, C₁₋₄ alkyl or C₁₋₄alkoxy, each R₅₃ is independently hydrogen, halo, cyano, C₁₋₄ alkyl,C₁₋₄ alkoxy, carboxy, sulfo or hydroxy, and Yo is a direct bond,--(CH₂)_(a) --, --O--, --S--, --SO₂ --, --NHCO--, --NHCONH--,--NHCO--(CH₂)_(b) --CONH--, --CONH--(CH₂)_(b) --NHCO--, --O--(CH₂)_(b)--O--, --N═N-- or --CH═CH--CO--CH═CH--,wherein B' is hydrogen, methyl,ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂,--(CH₂)_(b) --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖ or --A'--NH--R₂ ', wherein A'is linear or branched C₂₋₈ alkylene or phenylene,R₂ ' is ##STR323##wherein R₁₁ ' is hydrogen, chloro, nitro, methyl or methoxy,R₁₂ ' is--CO--(CH₂)_(t) --Z' or ##STR324## wherein R₁₃ ' is chloro, hydroxy,amino, N,N-di-(C₂₋₄ -hydroxyalkyl)amino, --NR₅ 'R₂₁, ##STR325## whereinR₁₁ ' is as defined above, R₁₄ ' is --NR₅ 'R₂₁, ##STR326## Z' is --N(R₇')₂ or --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, wherein R₇ ', R₈ ' and R₉ ' are asdefined below, andt is 1 or 2, wherein K₁ ' is ##STR327## wherein K_(b)is ##STR328## wherein R₂₉ is --(CH₂)_(m) --Z, ##STR329## wherein R₄₆ ishydrogen, --NHCO--(CH₂)_(b) --Z, --SO₂ NH--(CH₂)_(b) --Z, --CO--Y₁ --Zor ##STR330## each R₄₇ is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄alkoxy, nitro or cyano, andR₄₈ is C₁₋₄ alkoxy, R₃₂ is C₁₋₄ alkyl orphenyl, each R₃₃ is independently hydrogen, C₁₋₄ alkyl, --(CH₂)_(b)--OCH₃, 2-hydroxyethyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b) --N.sup.⊕(CH₃)₃ A.sup.⊖, R₃₄ is amino or hydroxy, R₃₅ is C₁₋₄ alkyl, --COOR₆,--CO--N(R_(5a))₂ or --CONH--Y₁ --Z, R₃₆ is hydrogen, ##STR331## whereinR₄₉ is hydrogen, --CONH--Y₁ --Z, --SO₂ NH--Y₁ --Z, --NHCO--(CH₂)_(b) --Zor ##STR332## and each R₅₀ is independently hydrogen, halo, C₁₋₄ alkoxy,C₁₋₄ alkyl, nitro or amino, R₃₇ is hydrogen, --NHCO--(CH₂)_(a) --Z,--SO₂ NH--Y₁ --Z, --CONH--Y₁ --Z, --CONHNH₂, --NH--Y₁ --Z, --CH₂ --Z,--NHNHCO--CH₂ --Z, nitrophenylcarbamoyl or ##STR333## R₃₈ is C₁₋₄ alkyl,benzyl or 2-cyanoethyl, R₃₉ is C₁₋₄ alkyl or --(CH₂)_(m) --Z, each R₄₀is independently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₆₃ is hydrogen,chloro, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or hydroxy, R₆₄ is hydrogen,dimethylamino, trimethylammonium A.sup.⊖, diethylamino, triethylammoniumA.sup.⊖, --CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂ --Z, --NHCO--Y₂ --Z, --SO₂NH--Y₂ --Z, --NHNHCO--CH₂ --Z or ##STR334## and B' is as defined above,K_(b) ' is ##STR335## wherein B' is as defined above, each R' isindependently methyl, ethyl, phenyl, benzyl or cyclohexyl, each R_(5a)is independently hydrogen or C₁₋₄ alkyl, each R₅ ' is independentlyhydrogen, methyl or ethyl, each R₅ " is independently hydrogen ormethyl, each R₆ is independently C₁₋₄ alkyl, each R₇ ' is independentlyhydrogen, C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl or--N(R₇ ')₂ is pyrrolidino, piperidino, morpholino, piperazino orN'-methylpiperazino, each R₇ " is independently hydrogen, methyl, ethylor 2-hydroxyethyl or --N(R₇ ")₂ is morpholino, piperidino, piperazino orN'-methylpiperazino, each R₈ ' is independently C₁₋₆ alkyl,n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl, and each R₉ ' isindependently methyl, ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ 'is pyridinium, pyridinium substituted by 1 or 2 methyl groups or##STR336## wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--,--SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, wherein R₆ isas defined above, andR'₉ is as defined above, each R₈ " is independentlymethyl, ethyl or 2-hydroxyethyl, and each R₉ " is independently methyl,ethyl or benzyl or --N.sup.⊕ (R₈ ")₂ R₉ " is pyridinium, pyridiniumsubstituted by 1 or 2 methyl groups or ##STR337## wherein R₉ ' and Zoare as defined above, each R₁₃ ' and R₁₄ ' is independently as definedabove,R₂₁ is C₁₋₁₂ alkyl; C₂₋₁₂ alkyl substituted by hydroxy; C₃₋₁₂alkyl interrupted by 1 to 3 radicals selected from --NR₇ -- and--N.sup.⊕ (R₈)₂ --A.sup.⊖ ; --NHCO--CH₂ --Z; --CH₂ --CONH--Y₁ --Z; --Y₁--Z; ##STR338## wherein R₂₃ is halo, hydroxy, nitro, C₁₋₄ alkyl or C₁₋₄alkoxy,R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖, --CO--Y₂ --Z',--NHCO--Y₂ --Z', --CONH--Y₂ --Z'--SO₂ NH--Y₂ --Z', --Y₂ --Z' or--NHNHCO--CH₂ --Z',wherein R₇ ', R₈ ' and R₉ ' are as defined above, andR_(5a) and R₆ are as defined above, R₂₁ ' is --(CH₂)_(b) --N(R₇")--(CH₂)_(b) --NR₇ "R₆ ', --(CH₂)_(b) --N.sup.⊕(R₈ ")₂ --(CH₂)_(b) 13N.sup.⊕ (R₈ ")₂ R₆ '2A.sup.⊖, --(CH₂)_(b) --N(R₇ ")--C₂ H₅, --(CH₂)_(b)--N.sup.⊖ (R₈ ")₂ --C₂ H₅ A.sup.⊖, --NHCO--CH₂ --Z", --CH₂ --CONH--Y₂''Z", ##STR339## wherein R₆ ' is methyl or ethyl,Y₂ ' is linear orbranched C₁₋₄ alkylene, and R₇ ", R₈ ", R₂₄ and Z" are as defined above,each R₂₆ is independently hydrogen, halo, nitro, amino, C₁₋₄ alkyl, C₁₋₄alkoxy, cyano, trifluoromethyl, phenyl, anilino, benzoyl, carbamoyl,phenoxy, halophenoxy, dihalophenoxy, C₁₋₄ alkylsulfonyl, phenylsulfonyl,C₁₋₄ alkylsulfonylamino or N,N-di(C₁₋₄ alkyl)sulfamoyl, each R₂₈ isindependently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,R₂₉ ' is--(CH₂)_(m') Z', ##STR340## wherein R₄₆ ' is hydrogen, --NHCO--(CH₂)_(b)--Z', --SO₂ NH--(CH₂)_(b) --Z' or ##STR341## wherein R₁₃ ' and R₁₄ " areas defined above, each R₄₇ ' is independently hydrogen, chloro, bromo,methyl, ethyl, methoxy, ethoxy, nitro or cyano, and R₄₈ ' is methoxy orethoxy, and each R₃₃ ' is independently hydrogen, 2-hydroxyethyl,3-methoxypropyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b) --N.sup.⊕ (CH₃)₃A.sup.⊖,R₃₄ is hydroxy or amino, R₃₆ ' is hydrogen, ##STR342## whereinR₄₉ ' is hydrogen, --CONH--(CH₂)_(m) '--Z', --NHCO--(CH₂)_(b) --Z' or##STR343## wherein R₁₃ ' and R₁₄ ' are as defined above, and each R₅₀ 'is independently hydrogen, chloro, methyl or methoxy, R₃₇ ' is##STR344## wherein R₁₃ " and R₁₄ " are as defined above, R₃₈ ' ismethyl, ethyl, 2-cyanoethyl or benzyl, R₃₉ ' is methyl, ethyl or--(CH₂)_(m) '--Z, R₄₀ is independently hydrogen, C₁₋₄ alkyl or C₁₋₄alkoxy, each T' is independently hydrogen, cyano, --CO--N(R₅ ')₂ or##STR345## wherein each R₃ ' is independently hydrogen, methyl, ethyl,amino or dimethylamino, andR₅ ' is as defined above, X' is--NH--CO--NH--, ##STR346## wherein R_(42a) is hydrogen, chloro, methylor methoxy,each R₄₃ is independently linear or branched C₁₋₄ alkylene,each R₄₄ is independently hydrogen or C₁₋₄ alkyl, R₄₅ is halo,2-hydroxyethylamino, N,N-di-(2-hydroxyethyl)amino, amino, hydroxy,--NH--(CH₂)_(b) --N(C₂ H₅)₂, N-methyl-N-phenylamino,N-cyclohexyl-N-methylamino, piperidino, methoxy or ethoxy, R_(45a) ischloro, 2-hydroxyethylamino, methoxy, ethoxy, hydroxy, amino,N,N-di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino,N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino or piperidino, and gis 1, 2, 3 or 4, X_(o) ' is --NH--, --NHCONH--, --NHCO--CH═CH--CONH--,--NHCO--(CH₂)_(b) --CONH--, ##STR347## wherein R₁₃ ' is as definedabove, each Y₁ is independently linear or branched C₁₋₈ alkylene orlinear or branched C₃₋₈ alkenylene, each Y₂ is independently linear orbranched C₁₋₈ alkylene, each Z' is independently as defined above, eachQ₁, Q₂, R₇, R₈, R₁₃, R₁₄ and Z is independently as defined in claim 1,each a is independently 1, 2 or 3, each b is independently 2 or 3, eachm is independently 1, 2, 3, 4, 5 or 6, each m' is independently 2, 3 or4, each n is independently 0, 1 or 2, each q is independently 0 or 1,and each A.sup.⊖ is independently a non-chromophoric anion,with theproviso that when R₁ "' is hydrogen, the compound is in metal-free form.8. A metal-free compound according to claim 1 having the formula##STR348## or a 1:1 or 1:2 metal complex thereof, or an acid additionsalt of a metal-free compound of said formula or an acid addition saltthereof,wherein A" is 1,2-ethylene, 1,3-propylene, 1,3-phenylene or1,4-phenylene, R₁ ^(iv) is hydrogen or --N═N--D"', whereinD"' is##STR349## wherein R₂₆ ' is hydrogen, nitro, chloro, methyl, methoxy orchlorophenoxy,each R_(26a) is independently nitro, chloro, methyl ormethoxy, each R_(27a) is independently hydrogen, chloro, methyl ormethoxy, and R_(27b) is hydrogen, methyl or methoxy, R₂ " is ##STR350##wherein R₁₂ " is --CO--CH₂ --Z" or ##STR351## wherein R₁₃ " is --NR₅"R₂₁ ', ##STR352## R₁₄ " is --NR₅ "R₂₁ ', ##STR353## and Z" is --N(R₇")₂ or --N.sup.⊕ (R₈ ")₂ R₉ "A.sup.⊖, andT" is cyano or ##STR354##wherein R₃ " is hydrogen or methyl, wherein A₁ ' is ##STR355## whereinR₅₁ is hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,R₅₂ is hydrogen,hydroxy, halo, cyano, --CONH₂, (C₁₋₄ alkyl)carbonylamino, --NHCONH₂,carboxy, sulfo, C₁₋₄ alkyl or C₁₋₄ alkoxy, each R₅₃ is independentlyhydrogen, halo, cyano, C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy, sulfo orhydroxy, and Yo is a direct bond, --(CH₂)_(a) --, --O--, --S--, --SO₂--, --NHCO--, --NHCONH--, --NHCO--(CH₂)_(b) --CONH--, --CONH--(CH₂)_(b)--NHCO--, --O--(CH₂)_(b) --O--, --N═N-- or --CH═CH--CO--CH═CH--, K_(a) "is ##STR356## wherein K_(b) ' is ##STR357## X", when both R_(27a) 's andR_(27b) are hydrogen, is a direct bond, --S--, --O--, --CH═CH--, --NH--,--NHCO--, ##STR358## or --CONH--(CH₂)₂ --NHCO--, whereinR_(42a) ishydrogen, chloro, methyl or methoxy, R₄₃ is linear or branched C₁₋₄alkylene, R_(45a) is chloro, 2-hydroxyethylamino, methoxy, ethoxy,hydroxy, amino, N,N-di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino,N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino or piperidino, and gis 1, 2, 3 or 4, andwherein B' is hydrogen, methyl, ethyl, hydroxyethyl,cyclohexyl, benzyl, --(CH₂)_(a) --N(R₇ ')₂, --(CH₂)_(b) --N.sup.⊕ (R₈')₂ R₉ 'A.sup.⊖ or --A'--NH--R₂ ', whereinA' is linear or branched C₂₋₈alkylene or phenylene, R₂ ' is ##STR359## wherein R₁₁ ' is hydrogen,chloro, nitro, methyl or methoxy, andR₁₂ ' is --CO--(CH₂)_(t) --Z' or##STR360## wherein R₁₃ ' is chloro, hydroxy, amino, N,N-di-(C₂₋₄-hydroxyalkyl)amino, --NR₅ 'R₂₁, ##STR361## wherein R₁₁ ' is as definedabove, R₁₄ ' is --NR₅ 'R₂₁, ##STR362## and Z' is --N(R₇ ')₂ or --N.sup.⊕(R₈ ')₂ R₉ 'A.sup.⊖, R' is methyl, ethyl, phenyl, benzyl or cyclohexyl,R₂₁ ' is --(CH₂)_(b) --N(R₇ ")--(CH₂)_(b) --NR₇ "R₆ ', --(CH₂)_(b)--N.sup.⊕ (R₈ ")₂ --(CH₂)_(b) --N(R₈ ")₂ R₆ '2A.sup.⊖, --(CH₂)_(b)--N(R₇ ")--C₂ H₅, --(CH₂)_(b) --N.sup.⊕ (R₈ ")₂ --C₂ H₅ A.sup.⊖,--NHCO--CH₂ --Z", --CH₂ --CONH--Y₂ '--Z", ##STR363## wherein R₆ ' ismethyl or ethyl,R₂₄ is --N(R₇ ')₂, --N.sup.⊕ (R₈ ')₂ R₉ 'A.sup.⊖,--CO--Y₂ --Z', --NHCO--Y₂ --Z', --CONH--Y₂ --Z'--SO₂ NH--Y₂ --Z', --Y₂--Z' or --NHNHCO--CH₂ --Z',wherein Z' is as defined above, Y₂ ' islinear or branched C₁₋₄ alkylene, and Z" is as defined above, each R₂₈is independently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₂₉ ' is--(CH₂)_(m') --Z', ##STR364## wherein R₄₆ ' is hydrogen,--NHCO--(CH₂)_(b) --Z', --SO₂ NH--(CH₂)_(b) --Z' or ##STR365## whereinR₁₃ ", R₁₄ " and Z' are as defined above, each R₄₇ ' is independentlyhydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy, nitro or cyano,andR₄₈ ' is methoxy or ethoxy, and each R₃₃ ' is independently hydrogen,2-hydroxyethyl, 3-methoxypropyl, --(CH₂)_(b) --N(CH₃)₂ or --(CH₂)_(b)--N.sup.⊕ (CH₃)₃ A.sup.⊖, R₃₄ is hydroxy or amino, R₃₆ ' is hydrogen,##STR366## wherein R₄₉ ' is hydrogen, --CONH--(CH₂)_(m') --Z',--NHCO--(CH₂)_(b) --Z' or ##STR367## wherein R₁₃ ', R₁₄ ' and Z' are asdefined above, and each R₅₀ ' is independently hydrogen, chloro, methylor methoxy, R₃₇ ' is ##STR368## wherein R₁₃ " and R₁₄ " are as definedabove, R₃₈ ' is methyl, ethyl, 2-cyanoethyl or benzyl, R₃₉ ' is methyl,ethyl or --(CH₂)_(m') --Z, R₄₀ is independently hydrogen, C₁₋₄ alkyl orC₁₋₄ alkoxy, and each T' is independently hydrogen, cyano, --CO--N(R₅')₂ or ##STR369## wherein each R₃ ' is independently hydrogen, methyl,ethyl, amino or dimethylamino,wherein each R₇ ' is independentlyhydrogen, C₁₋₆ alkyl, n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl or--N(R₇ ')₂ is pyrrolidino, piperidino, morpholino, piperazino orN'-methylpiperazino, each R₇ " is independently hydrogen, methyl, ethylor 2-hydroxyethyl or --N(R₇ ")₂ is morpholino, piperidino, piperazino orN'-methylpiperazino, each R₈ ' is independently C₁₋₆ alkyl,n-hydroxy(C₂₋₃ alkyl), benzyl or 2-cyanoethyl, and each R₉ ' isindependently methyl, ethyl, propyl or benzyl or --N.sup.⊕ (R₈ ')₂ R₉ 'is pyridinium, pyridinium substituted by 1 or 2 methyl groups or##STR370## wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--,--SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕ (R₆)₂ --A.sup.⊖, andR₉ ' is asdefined above, each R₈ " is independently methyl, ethyl or2-hydroxyethyl, and each R₉ " is independently methyl, ethyl or benzylor --N.sup.⊕ (R₈ ")₂ R₉ " is pyridinium, pyridinium substituted by 1 or2 methyl groups or ##STR371## wherein R₉ ' and Zo are as defined above,each R₁₃ ' and R₁₄ ' is independently as defined above,R₂₁ is C₁₋₁₂alkyl; C₂₋₁₂ alkyl substituted by hydroxy; C₃₋₁₂ alkyl interrupted by 1to 3 radicals selected from --NR₇ -- and --N.sup.⊕ (R₈)₂ --A.sup.⊖ ;--NHCO--CH₂ --Z; --CH₂ --CONH--Y₁ --Z; --Y₁ --Z; ##STR372## wherein R₂₃is halo, hydroxy, nitro, C₁₋₄ alkyl or C₁₋₄ alkoxy, andR₂₄ and Z' are asdefined above,wherein each R₅ ' is independently hydrogen, methyl orethyl, each R₅ " is independently hydrogen or methyl, each R_(5a) isindependently hydrogen or C₁₋₄ alkyl, each R₆ is independently C₁₋₄alkyl, each Y₁ is independently linear or branched C₁₋₈ alkylene orlinear or branched C₃₋₈ alkenylene, each Y₂ is independently linear orbranched C₁₋₈ alkylene, R₇, R₈, R₁₇, R₁₉ and Z as defined in claim 18,each a is independently 1, 2 or 3, each b is independently 2 or 3, eachm' is independently 2, 3 or 4, each n is independently 0, 1 or 2, each qis independently 0 or 1, each t is independently 1 or 2, and eachA.sup.⊖ is independently a non-chromophoric anion,with the proviso thatwhen R₁ ^(iv) is hydrogen, the compound is in metal-free form.
 9. Ametal-free compound according to claim 1 having the formula ##STR373##or a 1:1 or 1:2 metal complex thereof, or an acid addition salt of ametal-free compound of said formula or a 1:1 or 1:2 metal complexthereof,wherein one R₆₀ is hydroxy and the other is amino, R₆₁ ishydrogen, C₁₋₄ alkoxy or hydroxy, R₆₂ is hydrogen, chloro, nitro, C₁₋₄alkyl, C₁₋₄ alkoxy or hydroxy, R₆₃ is hydrogen, chloro, nitro, C₁₋₄alkyl, C₁₋₄ alkoxy or hydroxy, R₆₄ is hydrogen, dimethylamino,trimethylammonium A.sup.⊖, diethylamino, triethylammonium A.sup.⊖,--CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂ --Z, --NHCO--Y₂ --Z, --SO₂ NH--Y₂--Z, --NHNHCO--CH₂ --Z or ##STR374## wherein Y₂ is linear or branchedC₁₋₈ alkylene, each M is independently hydrogen or a non-chromophoriccation, and B, R, R₁₃, R₁₄, T, Z and A.sup.⊖ are as defined in claim1,with the provisos tht (i) the total number of cationic andprotonatable basic groups exceeds the number of sulfo groups by at leastone, and (ii) R₆₄ is in the 3- or 4-position of the ring to which it isattached.
 10. The compound according to claim 1 having the formula##STR375##
 11. The compound according to claim 1 having the formula##STR376##
 12. The compound according to claim 1 having the formula##STR377##
 13. The compound according to claim 1 having the formula##STR378##